catalysts

Article
Understanding of the Key Factors Determining the Activity and
Selectivity of CuZn Catalysts in Hydrogenolysis of Alkyl Esters
to Alcohols
Oleg Kikhtyanin 1, *, Jaroslav Aubrecht 2 , Violetta Pospelova 2 and David Kubička 1,2

1 Technopark Kralupy, University of Chemistry and Technology Prague, nám. G. Karse 7/2,
278 01 Kralupy nad Vltavou, Czech Republic; kubickad@vscht.cz
2 Department of Petroleum Technology and Alternative Fuels, University of Chemistry and Technology Prague,
Technická 5, Praha 6, 166 28 Dejvice, Czech Republic; aubrechj@vscht.cz (J.A.); pospelov@vscht.cz (V.P.)
* Correspondence: oleg.kikhtyanin@vscht.cz

Abstract: CuZn catalysts are perspective catalysts for esters hydrogenolysis, but more knowledge
is needed to optimize their catalytic performance. In this work, we consider the impact of CuZn
catalysts composition on their structure, activity, selectivity, and stability in esters hydrogenolysis.
Four catalysts with various Cu/Zn ratio were synthesized by a co-precipitation and characterized in
as-prepared, calcined, reduced, and spent state by XRF, XRD, N2 physisorption, CO2 -TPD, NH3 -TPD,
and N2 O chemisorption. XRD data revealed the effect of the composition on the size of Cu and ZnO
particles. The catalytic performance was investigated using an autoclave. All catalysts exhibited



high methyl hexanoate conversion about 48–60% after 3 h but their activity and selectivity were


found to be dependent on Cu/Zn ratio. The conversion of methyl hexanoate and hexyl hexanoate
Citation: Kikhtyanin, O.; Aubrecht, was compared to explain the observed product selectivity. Moreover, the catalysts stability was
J.; Pospelova, V.; Kubička, D. investigated in three consecutive reaction cycles and correlated with changes in the size of constituent
Understanding of the Key Factors
particles. Moreover, when different esters were tested, a slight decrease in conversion and increase in
Determining the Activity and
alcohol selectivity with a growth in molecule size was observed. Obtained results allow making a
Selectivity of CuZn Catalysts in
conclusion about the optimal composition that provides the good performance of CuZn catalysts in
Hydrogenolysis of Alkyl Esters to
ester hydrogenolysis.
Alcohols. Catalysts 2021, 11, 1417.
https://doi.org/10.3390/catal11111417
Keywords: ester hydrogenolysis; CuZn catalyst; transesterification; methyl hexanoate; hexyl hexanoate
Academic Editors: Angeliki A.
Lemonidou and Hiroto Yoshida

Received: 28 October 2021 1. Introduction

Accepted: 19 November 2021 The hydrogenolysis of carboxylic acid esters is a reaction of great commercial attrac-
Published: 22 November 2021 tiveness. It allows selective production of corresponding alcohols and their derivatives that
can further be used as raw materials in the production of surfactants, plasticizers, cosmetics,
Publisher’s Note: MDPI stays neutral and other chemicals [1–3]. For several decades, the process of obtaining alcohols from
with regard to jurisdictional claims in carboxylic acid esters has been based on employing traditional and highly efficient Adkins
published maps and institutional affil- catalysts, which include copper as an active metal and Cr2 O3 (ca. 40–50 wt%) [1,4]. The role
iations.
of the latter component is preventing Cu metallic particles from sintering and maintaining
their high dispersion during the catalytic process. Typically, the Adkins catalysts operate at
high temperatures (200–300 ◦ C) and hydrogen pressures (140–300 bar) [5]. Consequently,
great potential lies in finding catalytic formulations that would exhibit high activity in
Copyright: © 2021 by the authors. the hydrogenolysis of esters and high selectivity to alcohols when the process is carried
Licensee MDPI, Basel, Switzerland. out under milder reaction conditions. In addition, the synthesis of Adkins catalysts is
This article is an open access article accompanied by the formation of a large amount of Cr5+ and Cr6+ containing toxic wastes,
distributed under the terms and that are harmful to the environment [6,7]. Cr-free catalysts based on noble metals, i.e.,
conditions of the Creative Commons
Pd [8,9], Pt [10,11], Ru [12,13], and Rh [14], demonstrate good catalytic performance in the
Attribution (CC BY) license (https://
hydrogenolysis of esters to corresponding alcohols at mild reaction conditions. However,
creativecommons.org/licenses/by/
the high cost of such catalysts hinders their widespread industrial adoption. Therefore,
4.0/).

Catalysts 2021, 11, 1417. https://doi.org/10.3390/catal11111417 https://www.mdpi.com/journal/catalysts

Catalysts 2021, 11, 1417 2 of 20

non-noble metals have attracted much attention to be used as an active component in

catalysts for the production of alcohols from esters. Ni- and Co-based catalysts are active in
the hydrogenolysis of both the C-O and C-C bonds, provoking the occurrence of decarbony-
lation/decarboxylation reactions with the formation of hydrocarbons, thus resulting in a
decreased selectivity to target alcohols [15]. Copper-based catalysts, on the contrary, are se-
lective in the hydrogenolysis of the C-O bond and hydrogenation of the carbonyl group but
exhibit no activity in the hydrogenolysis of the C-C bond [16–22]. Thus, Cu-based catalysts
have a great potential for their use in the hydrogenolysis of esters to alcohols. Especially
this applies to bulk CuZn catalysts which are very effective in various applications, in par-
ticular in methanol synthesis from syngas [23–26]. The performance of CuZn catalysts has
been also investigated in the hydrogenolysis of different compounds, including glycerol to
propane-1,2-diol [27], dimethyl or diethyl succinate to butane-1,4-diol [20], hydrogenation
of succinic anhydride [28] and dimethyl adipate to 1,6-hexanediol [21,22,29]. The CuZn
catalysts were reported to be highly efficient in dimethyl adipate hydrogenolysis reaching
the dimethyl adipate conversion of 97% at the temperature of 205 ◦ C and 160 bar [21]. Our
previous research on the catalyst systems containing Cu as an active part promoted by
ZnO, Al2 O3 , and MgO showed that CuZn catalysts had the highest ester conversion and
selectivity to hexane-1,6-diol in the reaction of adipic acid dimethyl ester [30]. Moreover,
CuZn catalysts outperformed traditionally used CuCr catalysts, known as Adkins catalysts,
in the same reaction of dimethyl adipate hydrogenolysis making them a good candidate
to be the environmentally friendly alternative to CuCr catalysts [21] However, as far as
we are aware, no comprehensive work on the performance of such CuZn catalysts in the
hydrogenolysis of other carboxylic acid esters was reported. Several studies considered the
effect of Cu/Zn ratio on the structural characteristics and the performance of the catalysts,
and it was concluded that ester conversion increased with a growth in a copper surface
area [28] or with a decrease in a copper particle size [21]. In our recent article [30] we
have concluded that ZnO served as a structural promoter in CuZn catalysts for dimethyl
adipate hydrogenolysis that improves the properties of the catalysts by increasing BET
surface area and specific copper area as well as stabilizing Cu crystallites. However, ZnO
could not be considered as activity promoter, what was evidenced from the calculation of
TOF value for the CuZn catalyst. Nevertheless, there is an urgent need in receiving more
comprehensive information for a deeper understanding of how the Cu/Zn ratio affects not
only the activity, but also selectivity and stability of CuZn catalysts in the hydrogenolysis
of carboxylic acid esters.
Although the efficiency of CuZn catalysts for ester hydrogenolysis was confirmed, the
stability of such catalysts as well as their performance in hydrogenolysis of carboxylic acid
esters of different chain length were not extensively studied. The present study is focused
on comparing the activity, selectivity, and stability of CuZn catalysts varying in Cu/Zn
ratio in the hydrogenolysis of methyl hexanoate. A difference in the performance of the
catalysts was assessed by considering their physico-chemical properties, in particular by
determining the size of Cu and Zn particles in as-prepared, calcined, reduced, and spent
materials. In addition, to explain the observed dependence of product selectivity on the
reactant conversion, we compared the activity of the prepared catalysts in the conversion
of methyl hexanoate and hexyl hexanoate as an intermediate reaction product obtained by
a transesterification reaction. Finally, to the best of our knowledge, we are the first who
demonstrate the effect of carbon chain length in a reactant on the activity and selectivity of
CuZn catalysts by carrying out experiments with different methyl esters.

2. Results
2.1. Physico-Chemical Characterization
2.1.1. Chemical Analysis
Four CuZn-AP precursors with varying Cu/Zn ratios were prepared by a co-precipitation
method. XRF analysis evidenced that the obtained Cu/Zn ratios in the as-prepared precur-
sors were very close to the theoretical values estimated from the chemical composition of
Catalysts 2021, 11, 1417 3 of 20

the corresponding reaction mixtures used for the synthesis of the samples (Table 1). The
high efficiency of the used synthesis method was also confirmed by the colorless aqueous
filtrate obtained after separating a filter cake. It suggested that mostly all copper cations
from the initial nitrate solution were included into the composition of the precipitate.
Considering the XRF data, it could, therefore, be concluded that zinc cations were also
largely in the composition of the precipitate. Accordingly, the synthesis method used under
strictly controlled conditions should ensure a reproducible preparation of CuZn samples
with the desired chemical composition. It was also assumed that the chemical composition
of the samples did not change after calcination step.

Table 1. The physico-chemical characterization of CuZn as-prepared samples, calcined mixed oxides, and spent catalysts.

As-Prepared Samples Calcined Samples Spent Catalysts

Sample BET BET

Targeted CuO by XRF, ZnO by XRF, Cu/Zn Ratio Pore Volume, Pore Volume,
Surface Area, Surface Area,
Cu/Zn Ratio wt.% wt.% by XRF cm3 ·g−1 cm3 ·g−1
m2 ·g−1 m2 · g − 1
0.5CuZn 0.5 35.2 64.8 0.54 59 0.23 53 0.22
1CuZn 1 51.4 48.6 1.05 61 0.26 46 0.19
3CuZn 3 75.8 24.2 3.12 64 0.26 34 0.15
6CuZn 6 85.9 14.1 6.08 60 0.25 16 0.04

2.1.2. XRD Study

The phase composition from as-prepared catalyst precursors to the spent samples
was investigated using XRD (Figure 1). XRD patterns of the as-prepared materials are pre-
sented in Figure 1A. Samples 0.5CuZn-AP and 1CuZn-AP possessed aurichalcite structure
Cu2 Zn3 (CO3 )2 (OH)6 (ref. code 00-038-0152) which was characterized by typical reflections
at 2θ = 13.0◦ , 24.2, 34.1◦ , 41.9◦ , and 50.1◦ [22,31,32]. 3CuZn-AP and 6CuZn-AP contained
almost exclusively zincian malachite phase (Cu0.8 Zn0.2 )2 (OH)2 CO3 (ref. code 01-079-7851)
with characteristic reflections at 2θ = 14.8◦ , 17.6◦ , 24.1, or 31.9◦ [22,33]. In general, the results
from Figure 1A evidenced that almost phase-pure materials were prepared and used for
further characterization purposes, although the presence of other minor hydroxycarbonate
phases with a content of up to 5% could not be ruled out [33].
The calcination of the as-prepared precursors at T = 350 ◦ C resulted in the disap-
pearance of the reflections from hydroxycarbonate phases and the appearance of the
reflections from CuO and ZnO phases, which suggested the formation of mixed CuZn
oxides (Figure 1B). Previously it was reported that the complete decomposition of zincian
malachite phase to oxides occurred between 300 and 350 ◦ C, while a residual characteristic
diffraction peak at 2θ = 13.0◦ from aurichalcite phase could still be present in the XRD
patterns of an aurichalcite precursor after its calcination at 350 ◦ C [22]. In contrast, the XRD
patterns of the calcined samples prepared from CuZn precursors in the present study did
not show any reflexes from either aurichalcite or zincian malachite phase that suggested
total decomposition of the as-prepared hydroxycarbonates (Figure 1B). CuO and ZnO
crystallite size in the calcined samples with different Cu/Zn ratio was evaluated using the
Scherrer equation for reflections at 2θ ≈ 38.7◦ and 31.8◦ , respectively. Previously, it was
suggested that aurichalcite-derived catalysts had smaller Cu crystallites than the catalysts
derived from zincian malachite or copper-hydrozincite [34–36]. Nonetheless, some studies
indicated that there was no difference in the CuO particle size of the calcined samples as
a result of the precursor phase composition [31]. Similar to the latter study, no obvious
dependence of either CuO or ZnO crystallite size on the increase in Cu/Zn ratio was
observed for the samples prepared in the present study. Based on the XRD results, the
estimated size of the CuO crystallites in the mixed oxides was 5–6 nm, while that of the
ZnO crystallites was 6–7 nm (Figure 2).
 structure Cu2Zn3(CO3)2(OH)6 (ref. code 00-038-0152) which was characterized by typical
reflections at 2θ = 13.0°, 24.2, 34.1°, 41.9°, and 50.1° [22,31,32]. 3CuZn-AP and 6CuZn-AP
+ o
120,000 contained almost exclusively 120,000
C zincian malachite phase (Cu0.8Zn0.2)2(OH)2CO3 (ref.Dcode 01-
+
* - ZnO 079-7851) with characteristic reflections at 2θ* -=ZnO
14.8°, 17.6°, 24.1, or 31.9° [22,33]. In general,
0.5CuZn-R
+ - CuO
100,000 100,000 o - Cu phase-pure materials were 0.5CuZn-R*
the results from Figure
1CuZn-R1A evidenced that almost prepared4 and
Catalysts 2021, 11, 1417o - Cu O 1CuZn-R* of 20
2
used for further 3CuZn-R
characterization purposes, although * the presence of
* 3CuZn-R* minor hy-
other
80,000 6CuZn-Rwith a content
droxycarbonate phases 80,000
of up to 5% could not be o
ruled out [33].
6CuZn-R*
o
60,000 *+ 60,000
∗ + + B
a.u.

a.u.
*+* ∗ - AU
o + +
** + ∗ - ZnO
100,000 *
100,000
40,000
+ - ZM* * + * 0.5CuZn-AP 40,000 * * 0.5CuZn-C
∗ *+ - CuO
∗ 1CuZn-AP 1CuZn-C
20,000 + 3CuZn-AP 80,000
80,000 20,000 3CuZn-C
∗ 6CuZn-AP
∗ +
+ +
6CuZn-C
0
+∗
+ 0
60,000
60,000 ∗ 20 + +
40 60 80 20 ∗ 40 60 + 80
+ ∗ ∗ + + +

a.u.
+ +
a.u.

+
∗ ∗
2Theta, degrees ∗
∗2Theta, degrees + ∗ +
+ 40,000 + +∗ +
40,000
Figure 1. XRD patterns of the as-prepared CuZn precursors (A), calcined mixed oxides (B), samples reduced by a standard
method (C), samples reduced and treated with MeHe (D).
20,000 20,000

Catalysts 2021, 11, x FOR PEER REVIEW

The calcination of the as-prepared precursors at T = 350 °C resulted in the disappear- 4 of 21
0 ance of the reflections from hydroxycarbonate 0 phases and the appearance of the reflec-
20 40 60 80 20 40 60 80
tions from CuO and ZnO phases, which suggested the formation of mixed CuZn oxides
2 Theta, degrees 2 Theta, degrees
(Figure 1B). Previously it was reported that the complete decomposition of zincian mala-
120,000 +
chite
+ phase to oxides occurred C between 300 and 350 °C, while a residual characteristic
* - ZnO diffraction peak0.5CuZn-R
at 2θ = 13.0° from aurichalcite phase could still be present in the XRD
100,000 + - CuO
1CuZn-R
patterns of an aurichalcite precursor after its calcination at 350 °C [22]. In contrast, the
o - Cu2O
*
XRD patterns of 3CuZn-R
the calcined samples prepared from CuZn precursors in the present study
80,000 6CuZn-R
did not show any reflexes from either aurichalcite or zincian malachite phase that sug-
60,000
gested total decomposition of the as-prepared hydroxycarbonates (Figure 1B). CuO and
*
+ size
a.u.

*+*
ZnOo crystallite
+ ++ in the calcined samples with different Cu/Zn ratio was evaluated us-
40,000 ing the Scherrer equation for reflections at 2θ ≈ 38.7° and 31.8°, respectively. Previously,
* *+ *
it was suggested that aurichalcite-derived catalysts had smaller Cu crystallites than the
20,000 catalysts derived from zincian malachite or copper-hydrozincite [34–36]. Nonetheless,
some studies indicated that there was no difference in the CuO particle size of the calcined
0 samples as a result of the precursor phase composition [31]. Similar to the latter study, no
20 40 60 80
obvious dependence of either CuO or ZnO crystallite size on the increase in Cu/Zn ratio
2Theta, degrees
was observed for the samples prepared in the present study. Based on the XRD results,
Figure 1. XRD patterns of the
Figure 1. XRD patterns of the estimated CuZn
the as-prepared
as-prepared size of
CuZn the CuO(A),
precursors
precursors crystallites
(A), in the
calcined mixed
calcined mixed mixed
oxides
oxides oxides was
(B), samples
(B), samples 5–6by
reduced
reduced bynm, while that of
aa standard
standard
method (C), samples reduced the ZnO crystallites
and treated with was
MeHe 6–7
(D).
treated with MeHe (D). nm (Figure 2).

The calcination of the

Cu/CuO A as-prepared precursors at T =ZnO 350 °C resulted in the disappear-
B
C C
16 ance of theRreflections from hydroxycarbonate
16 phases and the appearance
R
of the reflec-
tions from AR CuO and ZnO phases, which suggested the formation ofARmixed CuZn oxides
(Figure 1B). Previously it was reported that the complete decomposition of zincian mala-
12 chite phase to oxides occurred between 12 300 and 350 °C, while a residual characteristic
Particle size, nm
Particle size, nm

diffraction peak at 2θ = 13.0° from aurichalcite phase could still be present in the XRD
patterns of an aurichalcite precursor after its calcination at 350 °C [22]. In contrast, the
8 XRD patterns of the calcined samples8prepared from CuZn precursors in the present study
did not show any reflexes from either aurichalcite or zincian malachite phase that sug-
gested total decomposition of the as-prepared hydroxycarbonates (Figure 1B). CuO and
4 4
ZnO crystallite size in the calcined samples with different Cu/Zn ratio was evaluated us-
ing the Scherrer equation for reflections at 2θ ≈ 38.7° and 31.8°, respectively. Previously,
0 it was suggested that aurichalcite-derived 0 catalysts had smaller Cu crystallites than the
0.5CuZn 1CuZn catalysts derived
3CuZn from
6CuZn zincian malachite or
0.5CuZncopper-hydrozincite
1CuZn [34–36].6CuZn
3CuZn Nonetheless,
some studies indicated that there was no difference in the CuO particle size of the calcined
Figure
Figure 2. The
2. The crystallite
crystallite size
size ofof CuOororCu
CuO Cu(A)
(A)and
andZnO
ZnO(B)
(B) determined
determined from
from XRD
XRDpatterns
patternsofofcalcined
calcinedmixed
mixedoxides (C),
oxides (C),
samples as a result of the precursor phase composition [31]. Similar to the latter study, no
reduced samples
reduced (R)(R)
samples andandspent
spentcatalysts
catalysts(AR).
(AR).
obvious dependence of either CuO or ZnO crystallite size on the increase in Cu/Zn ratio
was observed forcopper
The state of the samples
as well prepared
as the sizeinofthe present
copper and study. Based on
zinc particles the catalytic
before XRD results,
runs
the estimated size of the CuO crystallites in the mixed oxides
◦ was 5–6
were determined in CuZn mixed oxides reduced at 210 C. The measurement of metallic nm, while that of
the ZnOparticle
copper crystallites
sizewas
was6–7 nm (Figure
failed for the 2).
samples reduced by a standard method: after

Cu/CuO A ZnO C B
C
16 R 16 R
AR AR
 The state of copper as well as the size of copper and zinc particles before catalytic
runs were determined in CuZn mixed oxides reduced at 210 °C. The measurement of me-
tallic copper particle size was failed for the samples reduced by a standard method: after
being unloaded from the reactor, the reduced samples were immediately re-oxidized with
Catalysts 2021, 11, 1417 atmospheric oxygen which was evidenced by the obvious and significant heating 5 of 20of the
samples. As evidenced by their XRD patterns, most of the copper in the reduced samples
were present as CuO species with only residual presence of Cu and Cu2O (Figure 1C). To
prevent the re-oxidation of reduced copper species, CuZn samples were reduced at 210
being unloaded from the reactor, the reduced samples were immediately re-oxidized with
°C atmospheric
by a standard method
oxygen and
which was then treated by
evidenced with
theMeHe,
obviousas anddescribed
significant in heating
the Materials
of the and
Methods.
samples.XRD patterns by
As evidenced of the
theirreduced and treated
XRD patterns, most ofsamples
the copper (Figure 1D) showed
in the reduced samples that Cu
particles in theas
were present catalysts corresponded
CuO species to Cu0.presence
with only residual It suggested
of Cu that
and Cu (i) 2the total reduction
O (Figure 1C). To of
◦C
CuO species occurred at the reduction temperature of 210 °C and (ii) the treatment of the
prevent the re-oxidation of reduced copper species, CuZn samples were reduced at 210
by a reduced
freshly standard catalyst
method and withthen treated with
the organic MeHe, as
compound describedthe
prevented in the Materials of
re-oxidation and metal-
Methods. XRD patterns of the reduced
lic copper in air. Thus, the performed treatment and treated samples (Figure 1D) showed that
made it possible to assess the state of ZnO Cu
in the catalysts corresponded to Cu0 . It suggested that (i) the total reduction of
andparticles
Cu species in reduced CuZn catalysts just as at the beginning of a catalytic run. Figure
CuO species occurred at the reduction temperature of 210 ◦ C and (ii) the treatment of the
2A shows that the size of Cu species in the reduced and treated CuZn-R samples before a
freshly reduced catalyst with the organic compound prevented the re-oxidation of metallic
catalytic
copperrun was
in air. Thus,already larger in
the performed comparison
treatment made itwith the to
possible calcined
assess the CuZn-C
state of counterparts.
ZnO and
ThisCutrend
speciesbecame
in reducedmore pronounced
CuZn catalysts just withas increasing Cu/Zn
at the beginning of aratio in the
catalytic catalysts,
run. Figure 2Awhere
copper
showsparticle
that the size
sizeincreased fromin6.1
of Cu species nm
the to 12.6and
reduced nmtreated
for reduced
CuZn-R 0.5CuZn-R and 6CuZn-
samples before a
R, respectively.
catalytic run was Figure 2B evidences
already that the size
larger in comparison of the
with ZnO particles
calcined also changed
CuZn-C counterparts.after the
This trend
reduction became
step, more pronounced
regardless of the chemical with increasing
composition Cu/Zn ratio
of the in the catalysts,
catalysts, slightlywhere
increasing
copper particle size increased from 6.1 nm to 12.6 nm
from 10.3 nm to 12.8 nm with the increasing Cu/Zn ratio from 0.5 to 6. for reduced 0.5CuZn-R and 6CuZn-R,
respectively. Figure 2B evidences that the size of ZnO particles also changed after the
reduction step, regardless of the chemical composition of the catalysts, slightly increasing
2.1.3. Catalyst Surface Area
from 10.3 nm to 12.8 nm with the increasing Cu/Zn ratio from 0.5 to 6.
The textural properties of calcined and reduced samples were investigated using N2
2.1.3. CatalystThe
physisorption. Surface Area(Table 1) showed that the values of both BET surface area and
results
total pore
Thevolume showed no
textural properties of clear
calcineddependence
and reduced onsamples
the Cu/Zn
were ratio of calcined
investigated using CuZn-C
N2
physisorption. The results (Table 1) showed that the values of both BET
samples being in the range of 59–65 m ·g and 0.23–0.26 cm ·g , respectively. The simi-
2 −1 3 −1 surface area and
total
larity inpore volume
textural showed no
properties wasclear dependence
consistent withon the Cu/Zn
XRD ratio of
data, which calcined no
indicated CuZn-C
change in
samples being in the range of 59–65 m2 ·g−1 and 0.23–0.26 cm3 ·g−1 , respectively. The
CuO and ZnO particle size for CuZn-С samples regardless of a Cu/Zn ratio (Figure 2),
similarity in textural properties was consistent with XRD data, which indicated no change
which was also observed in our recent work [22]. The BET surface area of both CuO and
in CuO and ZnO particle size for CuZn-C samples regardless of a Cu/Zn ratio (Figure 2),
ZnO waswas
which loweralsoinobserved
comparison
in our with that
recent of the
work CuZn
[22]. mixed
The BET oxides
surface asofitboth
area wasCuO
shownandin our
recent article [37], also reflecting the effect of small size for the constituent
ZnO was lower in comparison with that of the CuZn mixed oxides as it was shown in our particles.
recent article [37], also reflecting the effect of small size for the constituent particles.
2.1.4. TPD of Adsorbed CO2 and NH3
2.1.4. TPD of Adsorbed CO2 and NH3
The acid-base sites of the calcined samples were probed using NH3-TPD and CO2-
The acid-base sites of the calcined samples were probed using NH -TPD and CO2 -
TPD. Figure 3 depicts the TPD profiles of NH3 and CO2 adsorbed on3 CuZn-C mixed ox-
TPD. Figure 3 depicts the TPD profiles of NH3 and CO2 adsorbed on CuZn-C mixed oxides,
ides, while Table 2 shows the number of both basic and acidic sites calculated from
while Table 2 shows the number of both basic and acidic sites calculated from the area
the
area under
under thethe obtained
obtained TPDTPD curves.
curves.

0.14 A 0.25 B

0.12
0.20
0.10 0.5CuZn-C
1CuZn-C
Signal, a.u.

Signal, a.u.

0.08 0.15 3CuZn-C

6CuZn-C
0.06
0.10
0.5CuZn-C
0.04 1CuZn-C
0.02
3CuZn-C 0.05
6CuZn-C
0.00
0.00
100 150 200 250 300 50 100 150 200 250 300
o o
T, C T, C

Figure 3. NH3 -TPD (A) and CO2 -TPD (B) spectra recorded for calcined CuZn samples varied in Cu/Zn ratio.
Catalysts 2021, 11, 1417 6 of 20

Table 2. The number of acid and basic sites determined from TPD profiles of adsorbed NH3 and
CO2 , respectively.

Sample Number of Acid Sites, mmol·g−1 Number of Basic Sites, mmol·g−1

0.5CuZn-C 0.135 0.176
1CuZn-C 0.136 0.187
3CuZn-C 0.168 0.237
6CuZn-C 0.151 0.190

The number of acid sites in calcined samples was in the range of 0.135–0.168 mmol g−1
and demonstrated an increasing trend with the growth of Cu/Zn ratio in CuZn-C samples
from 0.5 to 3 followed by a slight decrease for 6CuZn-C sample. The number of basic sites
in the calcined samples was in the range of 0.176–0.237 mmol g−1 and it demonstrated
similar dependence on Cu/Zn ratio: the largest concentration of basic sites was observed
for 3CuZn-C, while it slightly decreased for other catalysts. In our previous study, it was
shown that the concentration of both acidic and basic sites in CuZn mixed oxides was
larger than in single-phase ZnO or CuO [29], and it might be due to the high dispersion
of individual oxidic species. Therefore, a decrease in the acid-base characteristics of the
samples with either low or high Cu/Zn ratio, i.e., when approaching the pure CuO or ZnO
phase composition, was in line with the previous findings.

2.1.5. Specific Copper Surface Area

The specific copper surface area was determined using N2 O chemisorption. Prior to
N2 O chemisorption, CuZn-C mixed oxides were reduced, the reduction process was moni-
tored, and hydrogen consumption profiles were recorded. The curves of H2 consumption
during the reduction of CuO species in CuZn mixed oxides with different Cu/Zn ratio (see
the Supplementary Materials, Figure S1) evidenced that, regardless of the chemical com-
position of the samples, the reduction of constituent CuO species started at about 150 ◦ C.
The total amount of consumed H2 increased with the growth of Cu content in the samples,
while calculations showed that CuO content in the catalysts (Table 3) corresponded well
to the chemical composition of CuZn-AP precursors determined by XRF (Table 1), only
slightly overestimating the actual copper content. Thus, it was confirmed that all catalysts
were fully reduced prior to N2 O chemisorption experiments.

Table 3. H2 -TPR and N2 O chemisorption data for CuZn mixed oxides.

CuO Content Consumed H2 CuO Content (wt.%) SCu , SCu , Cu

Sample
(wt.%) by XRF (mmol·g−1 ) Calculated from Adsorbed H2 m2 ·gcat −1 m2 ·gCu −1 Dispersion, %
0.5CuZn-C 35.2 4.62 36.8 14.0 50 3.65
1CuZn-C 51.4 7.03 55.9 15.1 37 2.73
3CuZn-C 75.8 10.10 80.4 15.1 25 1.85
6CuZn-C 85.9 11.42 90.9 11.9 17 1.29

The specific surface area of copper was evaluated from the N2 O chemisorption experi-
ments with the reduced CuZn catalysts. The largest values of specific Cu surface area (SCu )
per gram of sample were determined for 1CuZn-R and 3CuZn-R, SCu = 15.1 m2 ·gcat −1 ,
while the lowest value was obtained for 6CuZn-R, SCu = 11.9 m2 ·gcat −1 (Table 3). The recal-
culation of the specific copper area per mass of copper demonstrated a definite declining
trend from SCu = 50 m2 ·gCu −1 to SCu = 17 m2 ·gCu −1 with the growth in the copper content
in the samples (Table 3). Accordingly, Cu dispersion calculated using a formula from [30]
also gradually decreased from 3.7% to 1.3% as the Cu/Zn ratio increased from 0.5 to 6. The
obtained Cu dispersion values correlated well with the values obtained in other studies on
Cu-containing catalysts [22,30,38–40].
 samples (Table 3). Accordingly, Cu dispersion calculated using a formula from [30] also
gradually decreased from 3.7% to 1.3% as the Cu/Zn ratio increased from 0.5 to 6. The
obtained Cu dispersion values correlated well with the values obtained in other studies
Catalysts 2021, 11, 1417
on Cu-containing catalysts [22,30,38–40]. 7 of 20

2.2. Catalysis
2.2.1. The Hydrogenolysis of Methyl Hexanoate (MeHe) in Presence of CuZn-R Catalysts
2.2. Catalysis
Varied in Cu/Zn Ratio
2.2.1. The Hydrogenolysis of Methyl Hexanoate (MeHe) in Presence of CuZn-R Catalysts
Thein
Varied four prepared
Cu/Zn Ratio catalysts and Zn-free Cu catalyst were tested in methyl hexanoate
hydrogenolysis (MeHe)catalysts
The four prepared at reaction
and temperature of 210
Zn-free Cu catalyst °C tested
were and pin = 10 MPa.
H2 methyl Figure 4A
hexanoate
depicts the change
hydrogenolysis in MeHe
(MeHe) conversion
at reaction in dependence
temperature ◦
of 210 C andon preaction time.Figure
All CuZn-R
4A de- cat-
H2 = 10 MPa.
pictsexhibited
alysts the changeainhigh
MeHe conversionof
conversion inMeHe
dependence on reaction
at chosen time.
reaction All CuZn-Rwhich
conditions, catalysts
signifi-
exhibited a high conversion of MeHe at chosen reaction conditions, which significantly
cantly exceeded that of a single-phase Cu catalyst (Figure 4A). In contrast, a single-phase
ZnOexceeded that possessed
catalysts of a single-phase
zero Cu catalyst
activity in (Figure 4A). In contrast,
the reaction. a single-phase
These results ZnO
unambiguously
catalysts possessed zero activity in the reaction. These results unambiguously proved the
proved the promoting effect of ZnO species in the CuZn-R catalysts for the hydrogenoly-
promoting effect of ZnO species in the CuZn-R catalysts for the hydrogenolysis of methyl
sis of methyl esters, as proposed in [30]. Figure 4A also evidenced that the catalysts per-
esters, as proposed in [30]. Figure 4A also evidenced that the catalysts performed differ-
formed differently
ently during duringconsequently
the reaction, the reaction,theconsequently
performancethe performance
of the catalysts at of
thethe catalysts at
beginning
theand
beginning and at the end of catalytic runs was
at the end of catalytic runs was compared separately. compared separately.

70 100
A B
MeHe
60
80
50
MeHe Conversion, %

0.5CuZn-R
Selectivity, %

40 60
1CuZn-R
0.5CuZn-R 3CuZn-R
30
1CuZn-R 40 6CuZn-R
3CuZn-R Cu-R
20
6CuZn-R
Cu-R 20
10
HeHe
0 0
0 30 60 90 120 150 180 0 10 20 30 40 50 60 70
Reaction time, min MeHe Conversion, %

C D
50 50

0.5CuZn-R
40 40 1CuZn-R
3CuZn-R
1-Heol Yield, %

HeHe Yield, %

6CuZn-R
30 30

0.5CuZn-R
20 1CuZn-R 20
3CuZn-R
10 6CuZn-R 10

0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
MeHe Conversion, % MeHe Conversion, %

Figure 4. (A)—Methyl
Figure 4. (A)—Methyl hexanoate
hexanoate(MeHe)
(MeHe)conversion
conversion inin dependence
dependenceon onreaction
reaction time
time forfor catalysts
catalysts withwith different
different Cu/ZnCu/Zn
ratio.ratio.
(B)—selectivity
(B)—selectivityto hexan-1-ol (1-Heol)
to hexan-1-ol (1-Heol)and andhexyl
hexyl hexanoate (HeHe)inindependence
hexanoate (HeHe) dependence on on MeHe
MeHe conversion.
conversion. (C)—The
(C)—The
yieldyield
of 1-Heol in dependence
of 1-Heol in dependence onon
MeHe
MeHeconversion.
conversion. (D)—The yieldofofHeHe
(D)—The yield HeHeinindependence
dependence on on MeHe
MeHe conversion.
conversion. Catalyst
Catalyst
weight—1.5
weight—1.5 g, MeHe
g, MeHeload—0.69
load—0.69mol,
mol,TTreac. =
reac.
210
= °C,
210 p
◦ C, H2
p =
H2
100
= bar.
100 bar.

Theactivity
The activity of
of CuZn-R
CuZn-Rcatalysts
catalysts at the
at initial 20 min
the initial 20ofmin
reaction was evaluated
of reaction in terms in
was evaluated
of initial reaction rate, r = n · g −1 ·min−1 , where n stands for the number of of
terms of initial reaction ini. rate, rMeHe
ini. = nMeHe·gcat ·min , where
cat −1 −1 nMeHe stands for the number
MeHe
MeHe mmoles consumed in this reaction time. The initial reaction
MeHe mmoles consumed in this reaction time. The initial reaction rate decreased in the rate decreased in the
following order 3CuZn-R > 6CuZn-R > 1CuZn-R > 0.5CuZn-R (Table 4). The growth of the
initial activity with the growth of Cu/Zn ratio in the catalysts from 0.5 to 3 appeared logical
as it concerned with the gradual growth of Cu content in the catalysts, i.e., with an increase
Catalysts 2021, 11, 1417 8 of 20

in the number of active sites. But the drop of the initial reaction rate observed for 6CuZn-R
with the largest Cu content should be considered in detail. To explain the obtained results,
it is necessary to consider XRD data for the CuZn samples before and just after a reduction
step. The size of both copper and zinc particles in CuZn-R samples considerably increased
in comparison with that in CuZn-C, and this effect became more evident with an increase in
the Cu/Zn ratio in the catalysts (Figure 2A). Therefore, the observed considerable sintering
of Cu species in 6CuZn-R occurred already at reduction step and, accordingly, the small
surface area of copper and its low dispersion (Table 3) were responsible for the decreased
initial activity of this catalyst in catalytic run. An increase in the size of copper particles
at reduction step in 3CuZn-R was less dramatic, which made it possible to maintain the
surface area and dispersion of copper at a relatively high level, 15.1 m2 ·g−1 and 1.85%,
respectively. As a consequence, the initial activity of the 3CuZn-R was higher than that
of 6CuZn-R (Table 4). With the similar surface area of copper in 1CuZn-R and 3CuZn-R,
the dispersion of copper in the former catalyst was larger, 2.73%. Nevertheless, the initial
activity of 1CuZn-R was lower than that of 3CuZn-R. Moreover, 0.5CuZn-R had a rather
large copper surface area and the highest Cu dispersion among all prepared samples, but
the initial activity of this catalyst was even lower than that of 6CuZn-R. The observed
discrepancy between the physico-chemical and catalytic results allowed assuming that
additional reasons could stand for the decreased initial activity of catalysts with a low
Cu/Zn ratio. The poor accessibility of the smaller metallic Cu particles within the excessive
ZnO species for the reactant molecules compared to bigger Cu particles could be assumed.

Table 4. Initial reaction rates and TOF values calculated for CuZn catalyst in MeHe hydrogenolysis.

MeHe Hydrogenolysis HeHe Hydrogenolysis

TOFMeHe /
Catalyst Initial Reaction Rate, TOF × 10−2 Initial Reaction Rate, TOF × 10−2 TOFHeHe
rini (nMeHe ·gcat −1 ·min−1 ) (s−1 ) rini (nHeHe ·gcat −1 ·min−1 ) (s−1 )
0.5CuZn-R 1.83 2.0 1.99 2.2 0.9
1CuZn-R 2.49 2.5 2.70 2.5 0.9
3CuZn-R 3.23 3.3 2.49 2.8 1.3
6CuZn-R 2.70 3.5 1.49 1.9 1.8

Additionally, the intrinsic activity of copper species in the catalysts varied in Cu/Zn
ratio could be evaluated considering their turnover frequency (TOF). Table 4 shows that
TOF gradually increased with the growth of Cu content in the catalysts. On the other
hand, an increase in the Cu/Zn ratio resulted in an increase in the copper particle size in
the reduced catalysts (Figure 2). The combination of these two trends allowed suggesting
that an increase in copper particle size in reduced catalysts contributed to TOF increase
for MeHe hydrogenolysis (Figure 5A). Thus, an increase in the Cu/Zn ratio in catalysts
from 0.5 to 3 resulted both in an increase in the number of copper particles, which was
reflected in an increase in the active copper surface area, and in an increase in the size
of such particles, which was promotional for an increase in TOF. Accordingly, the initial
activity reached the highest values for 3CuZn-R catalyst. A further increase in copper
content resulted in a further increase in the size of copper particles with high TOF value.
At the same time, the surface and dispersion of copper in 6CuZn-R significantly decreased,
and, accordingly, the initial activity of the 6CuZn-R catalyst also slightly decreased even at
the largest TOF value calculated for this catalyst.
With increasing reaction time, a difference in the performance of the catalysts became
obvious (Figure 4A): the larger the Cu/Zn ratio, the more pronounced drop in the activity
of the catalysts at the end of experiments. 0.5CuZn-R was the least active catalyst at
the beginning of the reaction but demonstrated the most stable activity with reaction
time, while 6CuZn-R with a high copper content was the least stable in the performance.
Despite the observed differences in the initial activity of 0.5CuZn-R, 1CuZn-R and 3CuZn-
R, the final MeHe conversion for these catalysts was approximately similar in the range of
 Catalysts 2021, 11, 1417 9 of 20

Catalysts 2021, 11, x FOR PEER REVIEW58–60% (Figure 4A). It could be assumed that the observed difference in the performance
9 of 20
of catalysts was concerned with a change in their properties during the reaction, which
was demonstrated by a change in the composition of reaction products.

3.6 A B
2.5
3.4

3.2
2.0
3.0

HeHe Yield, %
TOF*E (-)2, s (-)1

2.8 1.5

2.6
1.0 ZnO
2.4

2.2 0.5
2.0

1.8 0.0
6 7 8 9 10 11 12 13 10.0 10.5 11.0 11.5 12.0 12.5 13.0

Cu particle size, nm ZnO particle size, nm

Figure 5. (A).
Figure The
5. (A). dependence
The ofof
dependence TOF
TOFininMeHe
MeHehydrogenolysis
hydrogenolysis on
on the
the size of copper
size of copperparticles
particlesininreduced
reducedCuZn
CuZn catalysts.
catalysts.
(B).(B).
TheThe
dependence of HeHe yield in reaction between MeHe and 1-Heol on the size of ZnO particles in reduced
dependence of HeHe yield in reaction between MeHe and 1-Heol on the size of ZnO particles in reduced CuZn CuZn
catalysts and a single-phase ZnO.
catalysts and a single-phase ZnO.

With increasing
Previously, reaction
it was showntime, that athedifference in the performance
hydrogenolysis of the catalysts
of dimethyl adipate on CuZn became
cat-
obvious (Figure 4A):
alysts resulted in thethe larger the
formation of Cu/Zn ratio, theasmore
1,6-hexanediol pronounced
the targeted product dropandinabundant
the activity
ofby-products
the catalysts formed
at theby endtheoftransesterification
experiments. 0.5CuZn-Rreaction route,
was the withleast
otheractive
products beingatinthe
catalyst
minor amounts [21,22,29]. In case of MeHe hydrogenolysis,
beginning of the reaction but demonstrated the most stable activity with reaction only two main reaction prod-
time,
ucts were observed: hexan-1-ol (1-Heol) as the reaction product
while 6CuZn-R with a high copper content was the least stable in the performance. De- formed by hydrogenolysis
reaction
spite route, anddifferences
the observed hexyl hexanoate in the(HeHe) produced
initial activity of by transesterification
0.5CuZn-R, 1CuZn-R route
andbetween
3CuZn-R,
the final MeHe conversion for these catalysts was approximately similar in the depen-
MeHe and the formed 1-Heol. Figure 4B depicts selectivity to reaction products in range of
dence on reaction time for different CuZn catalysts. In all cases 1-Heol selectivity gradually
58–60% (Figure 4A). It could be assumed that the observed difference in the performance
decreased and, accordingly, HeHe selectivity increased during the experiments, which was
of catalysts was concerned with a change in their properties during the reaction, which
most pronounced for catalysts with a high Cu/Zn ratio, 3CuZn-R, and 6CuZn-R.
was demonstrated by a change in the composition of reaction products.
Figure 4C shows that the yield of 1-Heol was very similar for all studied catalysts at low
MeHe conversion withshown
Previously, it was a linearthat the hydrogenolysis
increasing of dimethyl
trend. With further growthadipate
in MeHeon CuZn cata-
conversion
lysts
the resulted in theofformation
linear growth 1-Heol yield of 1,6-hexanediol
was observed for as 0.5CuZn-R
the targeted product
and 1CuZn-R, andwhile
abundantin theby-
products
case of 3CuZn-R and 6CuZn-R an obvious deviation from a straight line was observed. On in
formed by the transesterification reaction route, with other products being
minor amounts
the other hand,[21,22,29].
HeHe yield In progressively
case of MeHeincreased
hydrogenolysis, only two
with a growth main reaction
in MeHe conversion,prod-
ucts
andwere
this observed:
trend washexan-1-ol
again the most (1-Heol) as the reaction
pronounced product
for 3CuZn-R formed
and 6CuZn-R by hydrogenolysis
(Figure 4D).
reaction route, change
The observed and hexyl in thehexanoate
yield of the(HeHe)
reactionproduced by transesterification
products suggested that the propertiesrouteofbe-
activeMeHe
tween sites in thethe
and catalysts
formed responsible
1-Heol. Figurefor hydrogenolysis and transesterification
4B depicts selectivity to reaction products routes in
differed. In order to explain the observed trends in the performance
dependence on reaction time for different CuZn catalysts. In all cases 1-Heol selectivity of the catalysts, the
XRD study of the samples after the reaction was carried out.
gradually decreased and, accordingly, HeHe selectivity increased during the experiments,
which A wascomparison in the size for
most pronounced of constituent particles
catalysts with a highin freshly
Cu/Zn
o
reduced and spentand
ratio, 3CuZn-R, catalysts
6CuZn-
R.evidenced that during the reaction an enlargement of Cu particles was observed, which
was the most obvious for catalysts with high Cu/Zn ratio. The size of copper particles
Figure 4C shows that the yield of 1-Heol was very similar for all studied catalysts at
in 6CuZn-R and 6CuZn-AR increased from 12.2 nm to 16.8 nm, while for 0.5CuZn-R and
low MeHe conversion with a linear increasing trend. With further growth in MeHe con-
0.5CuZn-AR this increase was only marginal, from 6.0 nm to 6.5 nm (Figure 2A). Therefore,
version the linearingrowth
the degradation of 1-Heol yield
the hydrogenolysis was observed
activity observedfor forCuZn
0.5CuZn-R
catalystsand 1CuZn-R,
with high
while in the case of 3CuZn-R and 6CuZn-R an obvious deviation
copper content could be explained by the gradual sintering of metallic copper particles from a straight line was
observed.
during the Onreaction.
the other hand,
These HeHethus
results yield progressively
provided additionalincreased
evidence with a growth
that in MeHe
the promoting
conversion, and this trend was again the most pronounced for
effect of zinc oxide particles was concerned with stabilizing copper particles, and it was3CuZn-R and 6CuZn-R
(Figure 4D). The observed
most pronounced change
for catalysts withina the
highyield
ZnO of the reaction
content, i.e., withproducts
Cu/Zn ratiosuggested that the
in the range
properties
of 0.5–1. of active sites in the catalysts responsible for hydrogenolysis and transesterifi-
cation routes differed. In order to explain the observed trends in the performance of the
catalysts, the XRD study of the samples after the reaction was carried out.
A comparison in the size of constituent particles in freshly reduced and spent cata-
lysts evidenced that during the reaction an enlargement of Cuo particles was observed,
which was the most obvious for catalysts with high Cu/Zn ratio. The size of copper parti-
Catalysts 2021, 11, 1417 10 of 20

In our recent article [37], we have shown that ZnO particles rather than metallic Cu0
were responsible for the occurrence of the transesterification reaction between the methyl
ester and the formed alcohol. In general, the transesterification reaction can proceed with
the participation of either acidic or basic sites [41–44]. Results from Table 2 suggest that the
number of both kinds of active sites in the CuZn catalysts increased with the growth in
the Cu/Zn atomic ratio from 0.5 to 3, followed by a slight decrease for 6CuZn-R sample.
From this point of view, the increased selectivity to HeHe with the increasing Cu/Zn ratio
from 0.5 to 3 was not surprising. Nevertheless, the largest selectivity to HeHe observed
for 6CuZn-R was hard to explain if considering exclusively the acid-base properties of the
catalyst. Then, in addition to the acid-base characteristics of the calcined CuZn-C samples,
other reasons for the observed trends in selectivity to hydrogenolysis and transesterification
products could be considered. First of all, the study of catalysts after the reaction using
N2 physisorption showed that both BET surface area and total pore volume of the spent
0.5CuZn-AR were similar to the values obtained for the freshly calcined 0.5CuZn-C, while
both the values were dramatically lower in case of 6CuZn-AR (Table 1). The observed trend
in the textural properties of the spent catalysts correlated well with their stability in the
reaction and with observed product selectivity. Indeed, the sintering of Cu particles may
contribute to a decrease in the total surface area. Additionally, the mesoporous space of the
spent catalysts with a high transesterification activity could be occupied by high-molecular
weight compounds which were not removed by a simple washing after the reaction.
To get additional information on the transesterification performance of CuZn catalysts,
experiments on the mutual processing of MeHe and 1-Heol mixture (2:1 mol/mol) at the
same reaction conditions were carried out (see the Supplementary Materials, Figure S2).
These experiments demonstrated that the yield of HeHe as a transesterification product
formed by a reaction between MeHe and 1-Heol increased with the growth of Cu/Zn ratio
in the CuZn-R catalysts. Among them, 6CuZn-R possessed a remarkable transesterification
performance (see the Supplementary Materials, Figure S2). For a comparison, the perfor-
mance of ZnO and reduced Cu catalysts in the conversion of MeHe and 1-Heol mixture was
also evaluated (both samples were prepared by the calcination of either Zn or Cu precursors
synthesized by the same recipe as was used for CuZn samples). Figure S2B depicts that
the yield of HeHe was larger on a single-phase ZnO as compared to CuZn-R catalysts.
It allowed suggesting that ZnO component in the CuZn-R catalysts was responsible for
the transesterification reaction route in methyl ester hydrogenolysis. Nevertheless, the
calculation of the corrected initial rate of HeHe formation based on ZnO content in the
catalysts showed that the activity in transesterification route increased with an increase in
Cu/Zn ratio in catalysts, and it was even larger for 6CuZn-R than that for a single-phase
ZnO (Table 5). Taking into account the XRD data (Figure 2B), the observed trend in the
transesterification performance correlated well with the size of ZnO particles in the cata-
lysts (Figure 5B). In addition, the performance of the single-phase ZnO sample also agreed
well with a general trend. Based on the obtained results it could be assumed that both the
acid-base properties of the CuZn catalysts and the size of the ZnO species were responsible
for the performance of CuZn-R catalysts in transesterification step.

Table 5. The initial rate of HeHe formation calculated for initial 40 min of a reaction between MeHe and 1-Heol on xCuZn-R
catalysts. The content of ZnO in the catalysts was taken from Table 1.

Corrected
ZnO Content in HeHe Yield (%) after Formation Rate,
Sample Formation Rate,
Catalysts, g 40 min mmolHeHe ·gcat −1 ·min−1
mmolHeHe ·gZnO −1 ·min−1
ZnO 0.75 4.45 0.82 0.82
0.5CuZn-R 0.97 1.40 0.13 0.20
1CuZn-R 0.72 1.46 0.13 0.28
3CuZn-R 0.36 1.89 0.17 0.73
6CuZn-R 0.20 3.61 0.33 2.43
 Catalysts 2021, 11, 1417 11 of 20

2.2.2. The Hydrogenolysis of Hexyl Hexanoate in Presence of CuZn-R Catalysts with

Different Cu/Zn Ratio
Considering the physico-chemical characteristics of CuZn, mixed oxides and their
change during the reaction may help in explaining the observed differences in MeHe
conversion and product selectivity. But these approaches could not shed light on reasons
for a successive increase in the content of HeHe as a transesterification reaction product.
The accumulation of HeHe among reaction products with reaction time was puzzling since
this compound, also being ester, should also be converted by hydrogenolysis. Therefore,
the hydrogenolysis reactivity of MeHe and HeHe should be compared under similar
reaction conditions.
Figure 6 demonstrates that, like MeHe, HeHe was effectively transformed by the
hydrogenolysis route in presence of all studied CuZn catalysts thus yielding two 1-Heol
molecules. HeHe conversion was in the range of 53–65% after 180 min, while a character
in the change of HeHe conversion also followed the dependence on Cu/Zn ratio in the
catalysts previously observed for MeHe hydrogenolysis. The initial activity of 1CuZn-R
and 3CuZn-R in HeHe hydrogenolysis was nearly similar (Table 4), but the activity of
the latter significantly slowed down during the reaction (Figure 6). On the other hand,
the initial activity of 0.5CuZn-R was lower, but HeHe conversion over this catalyst at
the end of the reaction exceeded 60%, i.e., approximately similar to that observed for the
most active 1CuZn-R. Finally, HeHe conversion over 6CuZn-R was the lowest indepen-
dently on reaction time (Figure 6). The comparison of TOF values for either MeHe or
HeHe hydrogenolysis showed that TOFMeHe /TOFHeHe ratio was only slightly below 1 for
0.5CuZn-R and 1CuZn-R, while they increased for 3CuZn-R and 6CuZn-R to 1.3 and 1.8,
correspondingly (Table 4). The performed calculations evidenced that catalysts with low
copper content demonstrated approximately similar performance in the hydrogenolysis of
the two esters, while MeHe was converted more effectively compared to HeHe on catalysts
with a high Cu/Zn ratio. The obtained TOFMeHe /TOFHeHe values allowed thus explaining
Catalysts 2021, 11, x FOR PEER REVIEW
the accumulation of HeHe among reaction products formed during MeHe hydrogenolysis
on 3CuZn-R and 6CuZn-R. However, the performance of catalysts with a low Cu/Zn ratio
requires an additional consideration.

70

60

50
HeHe Conversion, %

40
0.5CuZn-R
30 1CuZn-R
3CuZn-R
20 6CuZn-R

10

0
0 30 60 90 120 150 180
Reaction time, min
Figure6. 6.HeHe
Figure HeHe conversion in dependence
conversion on reaction
in dependence ontime for different
reaction CuZn
time for catalysts. CuZn
different HeHe catalys
load—138.2 g (0.69 mol), catalyst weight—1.5 g, T = 210 ◦ C, p = 100 bar.
load—138.2 g (0.69 mol), catalyst weight—1.5 g, Treac. =H2
reac. 210 °C, pH2 = 100 bar.

The activity of 1CuZn-R catalyst in the simultaneous conversion of MeHe an

mixture with different MeHe/HeHe ratio (100/0, 85/15, 70/30, 50/50, 30/70, 15/
 Figure 6. HeHe conversion in dependence on reaction time for different CuZn catalys
load—138.2 g (0.69 mol), catalyst weight—1.5 g, Treac. = 210 °C, pH2 = 100 bar.

Catalysts 2021, 11, 1417 12 of 20

The activity of 1CuZn-R catalyst in the simultaneous conversion of MeHe an
mixture with different MeHe/HeHe ratio (100/0, 85/15, 70/30, 50/50, 30/70, 15
0/100) was studied under the same reaction conditions. The conversion of the tw
The activity of 1CuZn-R catalyst in the simultaneous conversion of MeHe and HeHe
was calculated based on their content in the initial MeHe/HeHe mixtures and a
mixture with different MeHe/HeHe ratio (100/0, 85/15, 70/30, 50/50, 30/70, 15/75, and
min ofwas
0/100) thestudied
reaction.
underThe
theconversion
same reactionof the MeHe
conditions. constantly
The conversion increased with decre
of the two esters
content
was in the
calculated reaction
based mixture
on their content inthus reflecting
the initial a concentration
MeHe/HeHe mixtures andeffect
after (Figure
180 min 7). In c
of
thethe reaction. The
conversion conversion
of HeHe of the MeHe
gradually constantly
decreased withincreased
decreasingwith its
decreasing
contentits (or with
content in the reaction mixture thus reflecting a concentration effect (Figure 7). In contrast,
ing the MeHe content) in the MeHe/HeHe mixture. Moreover, at MeHe/HeHe mo
the conversion of HeHe gradually decreased with decreasing its content (or with increasing
of 85/15
the MeHe the conversion
content) of HeHe mixture.
in the MeHe/HeHe had a negative
Moreover,value (Figure 7):
at MeHe/HeHe thisratio
molar couldof be inte
as its the
85/15 additional
conversionformation
of HeHe hadfrom MeHe value
a negative by transesterification
(Figure 7): this couldreaction route rather
be interpreted
as its additional formation from MeHe by transesterification reaction
conversion by hydrogenolysis route. Consequently, a decrease in HeHe route rather than its conve
conversion by hydrogenolysis route. Consequently, a decrease in HeHe conversion
other experiments could also be partially explained by the formation of this com in other
experiments could also be partially explained by the formation of this compound upon the
upon the interaction of MeHe with the formed 1-Heol.
interaction of MeHe with the formed 1-Heol.

MeHe
80 HeHe

60
Conversion, %

40

20

0
100/0 85/15 70/30 50/50 30/70 15/85 0/100
Me-He/He-He molar ratio
Figure 7. The simultaneous conversion of MeHe and HeHe in their mixture over 1CuZn catalyst. The
total amount of esters (MeHe + HeHe) taken for the reaction—0.69 mol, mcat = 1.5 g, Treac. = 210 ◦ C,
pH2 = 100 bar.

Nevertheless, it should be kept in mind that MeHe was converted to 1CuZn-R predom-
inantly to 1-Heol, rather than to HeHe (Figures 4C and 5D). Therefore, both the absence
of HeHe conversion at a low HeHe content in the mixture (MeHe/HeHe = 85/15) and
a decrease in the HeHe conversion even at a low MeHe content (MeHe/HeHe = 15/85)
might also mean that the smaller-size MeHe could introduce an inhibition effect on the
conversion of bigger-size HeHe.
This assumption could explain trends in the change of product selectivity observed during
the hydrogenolysis of dimethyl adipate (DMA) from our recent studies [21,22,30,37,45,46].
Indeed, selectivity to 1,6-hexanediol was below 20% in a broad range of DMA conversion
and it sharply increased only at DMA conversion approaching 100% [37]. Similarly, it
was found in a long-time experiment with MeHe as a feed that selectivity to 1-Heol
constantly decreased and, in opposite, the selectivity to HeHe increased along with the
growth in MeHe conversion up to ≈80%, followed by a sharp increase in 1-Heol selectivity
at the expense of the HeHe selectivity (Figure 8). The results suggested that during the
hydrogenolysis of methyl esters in presence of CuZn catalysts, a high selectivity to alcohols
 [37]. Similarly, it was found in a long-time experiment with MeHe as a feed that selectivity
to 1-Heol constantly decreased and, in opposite, the selectivity to HeHe increased along
with the growth in MeHe conversion up to ≈80%, followed by a sharp increase in 1-Heol
Catalysts 2021, 11, 1417 selectivity at the expense of the HeHe selectivity (Figure 8). The results suggested 13 of 20 that
during the hydrogenolysis of methyl esters in presence of CuZn catalysts, a high selectiv-
ity to alcohols could not be reached until almost the total conversion of the initial ester
was could
achieved
not beand, consequently,
reached thetotal
until almost the consumption ofthe
conversion of a transesterification product
initial ester was achieved and, would
exceed its formation.
consequently, the consumption of a transesterification product would exceed its formation.

100 A 100
B

80 80
MeHe Conversion, %

60 MeHe

Selectivity, %
60
HeHe

40 40

20 20

0 0
0 60 120 180 240 300 360 420 0 20 40 60 80 100

Reaction time, min. MeHe Conversion, %

Figure 8.Figure
MeHe conversion
8. MeHe (A) and
conversion selectivity
(A) and totoreaction
selectivity reaction products
products (B)(B)observed
observedin ainlong-time
a long-time experiment
experiment on 1CuZn-R
on 1CuZn-R
catalyst.catalyst. The amount
The amount of MeHe—0.69
of MeHe—0.69 mol,mol, m=cat3.0
mcat = 3.0 g,reac.
g, T Treac.
= 210 °C,◦ C,
= 210 pH2pH2 = 100bar.
= 100 bar.

2.2.3.2.2.3.
TheThe Stability
Stability ofofCuZn
CuZnCatalysts
Catalysts in
inRepeating
RepeatingReaction Cycles
Reaction Cycles
To evaluate the effect of Cu/Zn ratio on the stability of CuZn catalysts in repeated
To evaluate the effect of Cu/Zn ratio on the stability of CuZn catalysts in repeated
MeHe hydrogenolysis cycles, a reaction mixture after the completion of the first catalytic
MeHe runhydrogenolysis
was removed fromcycles, a reaction
an autoclave mixture
through after
an outlet thefollowed
valve, completion
by theof the first
addition of acatalytic
run was removed from an autoclave through an outlet valve, followed by
Catalysts 2021, 11, x FOR PEER REVIEWfresh reactant into the reactor. Figure 9 demonstrates MeHe conversion obtained in three
the addition
14 of 20
of
a fresh reactantcatalytic
consecutive into theruns
reactor. Figure
(A) and 9 demonstrates
selectivity to 1-Heol atMeHe
the endconversion obtained
of each experiment inin three
dependence on the Cu/Zn ratio in the catalysts.
consecutive catalytic runs (A) and selectivity to 1-Heol at the end of each experiment in
70
dependence on the Cu/Zn ratio in the 90
catalysts.
A 1 B
80 2
60 1 3
2 70
50 3
MeHe Conversion, %

1-Heol Selectivity, %

60
40 50

30 40

30
20
20
10
10

0 0
0.5CuZn-R 1CuZn-R 3CuZn-R 6CuZn-R 0.5CuZn-R 1CuZn-R 3CuZn-R 6CuZn-R

Figure 9. MeHe
Figure conversion
9. MeHe conversionobserved after180
observed after 180min min in three
in three consecutive
consecutive runs (numbers
runs (numbers 1, 2, and 31,stand
2, and 3 stand
for the for the corre-
corresponding
sponding reaction
reaction runs)
runs) in in presence
presence of CuZn of CuZn(A)
catalysts catalysts (A) andtoselectivity
and selectivity to 1-Heol
1-Heol at MeHe at MeHe
conversion conversion
of 40% of 40%
(B). Catalyst (B). Cata-
weight—
lyst weight—1.5 g, MeHe load—0.69
1.5 g, MeHe load—0.69 210 ◦TC,
mol, Treac. =mol, pH2
reac. = 210 °C,bar.
= 100 pH2 = 100 bar.

Catalystswith
Catalysts withlower
lower Cu
Cu content,
content,0.5CuZn
0.5CuZnand and1CuZn,
1CuZn, demonstrated
demonstratedstable perfor-
stable perfor-
mance in three consecutive runs of MeHe hydrogenolysis. In contrast, MeHe conversion
mance in three consecutive runs of MeHe hydrogenolysis. In contrast, MeHe conversion
gradually decreased in repeating reaction cycles in case of catalysts with higher Cu content,
gradually decreased
and the decrease in repeating
in MeHe reaction
conversion cycles
was the mostinsignificant
case of catalysts with(Figure
for 6CuZn-R higher9A).
Cu con-
tent, and the
Indeed, decrease from
as evidenced in MeHe
XRD conversion
data, several was the cycles
reaction most significant for 6CuZn-R
resulted in further (Figure
growth in
9A). Indeed, as evidenced from XRD data, several reaction cycles resulted in further
growth in the size of Cu particles in spent catalysts after the third cycle, 3CuZn-AR3 and
6CuZn-AR3 (see the SI, Figure S3), so the gradual decline of their hydrogenolysis perfor-
mance could be assumed. Nevertheless, the selectivity to 1-Heol at similar MeHe conver-
sion did not change to a great extent in experiments for all the catalysts (Figure 9B) which
 Catalysts 2021, 11, 1417 14 of 20

the size of Cu particles in spent catalysts after the third cycle, 3CuZn-AR3 and 6CuZn-AR3
(see the Supplementary Materials, Figure S3), so the gradual decline of their hydrogenolysis
performance could be assumed. Nevertheless, the selectivity to 1-Heol at similar MeHe
conversion did not change to a great extent in experiments for all the catalysts (Figure 9B)
which was consistent with a very small change in size of ZnO particles during the consec-
utive reaction runs (see the Supplementary Materials, Figure S3). The presented results
evidence that CuZn catalysts with the Cu/Zn ratio of 0.5 to 1 demonstrate the remarkable
performance in terms of activity, selectivity, and stability in the MeHe hydrogenolysis.

2.2.4. The Hydrogenolysis of Methyl Esters with the Different Length of Carbon Chain
In previous sections we have compared the performance of CuZn catalyst in the
hydrogenolysis of two esters with the same C6 acid radical but varied in alcohol radical,
i.e., MeHe and HeHe. Consequently, the effect of the size of alkyl chain length in methyl
esters on their conversion should also be elucidated. The hydrogenolysis activity of
1CuZn-R catalyst was compared in experiments with methyl hexanoate (MeHe), methyl
octanoate (MeOc), methyl laurate (MeLa), and methyl stearate (MeSte). As evidenced from
Figure 10A, ester conversion in presence of 1CuZn catalyst gradually decreased from ≈60%
in case of both methyl hexanoate and methyl octanoate to ≈47% for methyl stearate. The
observed decline in the ester conversion with the growth of a carbon chain could probably
be concerned with the increasing struggle of larger molecules for active sites on a catalyst
surface. Nevertheless, at the same ester conversion, alcohol selectivity slightly increased
with an increase in the carbon chain length (Figure 10B), that could be explained by either a
difficulty for large molecules to interact with each other or by the increased hydrogenolysis
activity of the resulting ester. Therefore, hydrogenolysis of ester molecules with the
increased length of carbon chain prevailed compared with the transesterification step
with the participation of two bulky molecules. Nevertheless, the performed experiments
evidence the outstanding catalytic performance of CuZn catalysts in the hydrogenolysis
Catalysts 2021, 11, x FOR PEER REVIEW 15 of 20
of methyl esters varied in their size that allow producing corresponding alcohols with
high selectivity.

A 100
B
60
90

50 80
Ester Conversion, %

Alcohol selectivity, %

70
40 60

50
30
40
20 30

20
10
10
0 0
MeHe MeOc MeLa MeSte MeHe MeOc MeLa MeSte
Methyl ester Methyl ester

Figure 10.10.
Figure (A)(A)Catalytic
Catalyticperformance
performanceofof1CuZn
1CuZn catalyst
catalyst in the hydrogenolysis
hydrogenolysisofofmethyl
methylesters
estersvaried
varied in in
thethe length
length of aof a
carbon chain. (B) Alcohol selectivity at ester conversion of ≈45%. T = 210◦ °C, p = 100 bar, reaction
carbon chain. (B) Alcohol selectivity at ester conversion of ≈45%. T = 210 C, pH2 = 100 bar, reaction time—3 h, catalyst
H2 time—3 h, catalyst
weight—1.5
weight—1.5 g,g,ester
esterload—0.69
load—0.69 mol (in case
mol (in caseofofexperiment
experiment with
with Me-Ste
Me-Ste catalyst
catalyst weight
weight was reduced
was reduced to while
to 0.5 g, 0.5 g,0.23
while
mol0.23
molofof the
the ester
ester was was dissolved
dissolved in decalin),
in decalin), Treac.Treac.
= 210= 210
◦ C,°C,
pH2pH2 = 100
= 100 bar.
bar.

3.3.Materials
Materialsand
andMethods
Methods
3.1.Preparation
3.1. PreparationofofCatalysts
Catalysts
Precursorsfor
Precursors forCuZn
CuZn catalysts
catalysts with
withdifferent
differentcopper-to-zinc
copper-to-zinc ratio from
ratio 0.50.5
from to 6.0 were
to 6.0 were
prepared by a co-precipitation method based on a recipe described in [21]. An aqueous
prepared by a co-precipitation method based on a recipe described in [21]. An aqueous
solution of copper and zinc nitrates, Cu(NO3)2·3H2O (99.0%, Penta, s.r.o., Prague, Czech
Republic) and Zn(NO3)2·6H2O (99.6%, Lach:ner, s.r.o., Neratovice, Czech Republic), in a
proportion to obtain the desired Cu/Zn ratio and the total concentration of 0.5 mol·l−1 and
an aqueous solution of a precipitant Na2CO3 (99.4%, Lach:ner, s.r.o.) with the concentra-
tion of 1.0 mol·L−1 were simultaneously dosed into a beaker containing distilled water pre-
Catalysts 2021, 11, 1417 15 of 20

solution of copper and zinc nitrates, Cu(NO3 )2 ·3H2 O (99.0%, Penta, s.r.o., Prague, Czech
Republic) and Zn(NO3 )2 ·6H2 O (99.6%, Lach:ner, s.r.o., Neratovice, Czech Republic), in a
proportion to obtain the desired Cu/Zn ratio and the total concentration of 0.5 mol·L−1 and
an aqueous solution of a precipitant Na2 CO3 (99.4%, Lach:ner, s.r.o.) with the concentration
of 1.0 mol·L−1 were simultaneously dosed into a beaker containing distilled water pre-
heated to 60 ◦ C. The temperature of the precipitation was 60 ◦ C, the flow rate of the mixed
salt solution was fixed while that of the precipitant solution was continuously adjusted by
changing the pump performance to keep a constant pH value of 7 ± 0.1. After completing
the precipitation, the mixture was aged for 90 min, the obtained precipitates were filtered,
then washed with distilled water and finally, the wet cakes were dried at 60 ◦ C for 24 h.
The produced as-prepared precursors were further named as xCuZn-AP, where x stands
for Cu/Zn ratio. Calcined samples were produced by the calcination of the precursors at
350 ◦ C in air for 3 h, and named as xCuZn-C.

3.2. Catalyst Characterization

The phase composition of prepared samples and the particle size of the relevant phases
present in the catalysts were determined by X-ray diffraction using a diffractometer PANan-
alytical X’Pert3 Powder (Malvern Panalytical Ltd., Malvern, UK) and Cu Kα radiation. The
XRD patterns were recorded in a range of 2θ = 5◦ –70◦ . The crystallite sizes were calculated
using the Scherrer’s equation, and reflections at 2θ ≈ 31.8◦ , 43.3◦ , and 38.6◦ were used for
the particle size calculations for ZnO, Cu, and CuO, respectively [47].
The copper and zinc content in the catalyst precursors was analyzed by XRF using a
ARL 9400 XP spectrometer (Thermo ARL, Switzerland) equipped with a rhodium lamp.
It was assumed that the Cu/Zn ratio remained the same after the calcination step. The
absence of Cu or Zn leaching was confirmed by the analysis of liquid reaction products
by AAS using Agilent 280FS AA (Agilent Technologies, Santa Clara, CA, USA), where a
mixture of acetylene and air was used as an atomization flame.
Nitrogen physisorption was measured at 77 K using a static volumetric adsorption
system (TriFlex analyzer, Micromeritics, Norcross, GA, USA). The samples were degassed
at 473 K (12 h) prior to N2 adsorption analysis to obtain a clean surface. The obtained
adsorption isotherms were fitted using the Brunauer-Emmett-Teller (BET) method for
specific surface area and the BJH method for the distribution of mesopores. The copper
surface area was measured by the RFC technique carried out on an Autochem II 2920
(Micromeritics Instrument Corp., Norcross, GA, USA) connected on-line to an RGA 200
quadrupole mass spectrometer (Prevac, Rogów, Poland). The details of the measurements
were described previously [21,22].
Temperature-programmed desorption (TPD) of CO2 and NH3 was carried out using a
Micromeritics Instrument, AutoChem II 2920 (Micromeritics Instrument Corp., Norcross,
GA, USA) equipped with a thermal conductivity detector (TCD) and a quadrupole mass
spectrometer MKS Cirrus 2 Analyzer (MKS Instruments, Inc., Andover, MA, USA). Prior
to adsorption of CO2 , a catalyst was heated under a helium flow (50 mL·min−1 ) up to
300 ◦ C and kept at this temperature for 60 min to remove impurities from the sample. In
the following step, the sample was cooled down to an adsorption temperature of 25 ◦ C and
treated with a flow of CO2 /He (50%) for 30 min. Then the sample was purged with helium
for 90 min to remove physisorbed CO2 . Afterwards, the linear temperature program
(10 ◦ C·min−1 ) was started at a temperature of 25 ◦ C and the sample was heated up to a
temperature of 450 ◦ C. In experiments on NH3 adsorption, a catalyst was heated under
a helium flow (50 mL·min−1 ) up to 300 ◦ C and kept at this temperature for 60 min to
remove impurities from the sample. In the following step, the sample was cooled down
to an adsorption temperature of 70 ◦ C and treated with a flow of NH3 /He (2.5%) for
30 min. Then the sample was purged with helium for 105 min to remove physisorbed NH3 .
Afterwards, the linear temperature program (10 ◦ C·min−1 ) was started at a temperature of
70 ◦ C and the sample was heated up to a temperature of 450 ◦ C.
Catalysts 2021, 11, 1417 16 of 20

3.3. Catalyst Testing

All catalytic experiments on the hydrogenolysis of carboxylic acid methyl esters
were carried out in a Parr stainless steel autoclave with a reactor volume of 300 mL.
Methyl hexanoate (MeHe, SigmaAldrich, ≥99%, Merck Life Science spol. s r.o., Prague,
Czech Republic), hexyl hexanoate (HeHe, SigmaAldrich, ≥97%), methyl octanoate (MeOc,
SigmaAldrich, 99%), methyl laurate (MeLa, SigmaAldrich, ≥98%) and methyl stearate
(MeSte, SigmaAldrich, ≥96%) were used as reactants for the tests. Before a catalytic
experiment, a calcined catalyst (usually 1.5 g) was loaded into the autoclave and reduced
in situ at 210 ◦ C using H2 (99.9%, SIAD Czech, s.r.o., Prague, Czech Republic). The state of
copper and the size of both Cu and Zn particles after the reduction step were determined by
unloading the reduced samples from the autoclave. To prevent the re-oxidation of metallic
copper species with oxygen in air, hydrogen was replaced with nitrogen after completing
the reduction step, the reactor was cooled down to room temperature, methyl hexanoate
was added to the reduced sample, and the mixture was stirred for 30 min. Then the sample
was separated from the excess of methyl hexanoate by filtration, washed with acetone
and dried in ambient temperature. The reduced and treated samples were further named
as xCuZn-R.
To start a catalytic experiment, after the reduction step and autoclave cooling, 0.69 mol
of a methyl ester was loaded into the reactor. In case of methyl stearate, the mixture of
the ester with decalin (decahydronaphthalene, mixture of isomers, Aldrich, 98%) in the
volume ratio of 1:2 was used. The reaction temperature was kept at 210 ◦ C, while the
hydrogen pressure was kept at 100 bar. The effect of both internal and external diffusion
was evaluated by performing catalytic experiments with varying stirring rates and catalyst
weights (see the Supplementary Materials, Table S1). Based on these results the stirring
rate was kept at 600 RPM. Liquid reaction products were periodically (5, 10, 20, 40, 60, 90,
120, 180 min) withdrawn from the reactor during the experiment, diluted with acetone
(1:25 V/V) and analyzed by an Agilent 7820 GC-FID (Agilent Technologies, Santa Clara,
CA, USA) using a HP-5 capillary column, 30 m length, 0.32 mm i.d., 0.25 µm thick.
The conversion of methyl esters was evaluated using Equation (1). Due to the absence
of cracking reactions (confirmed by the GC analysis of the products), product selectivity was
calculated using Equation (2). Methanol was excluded from a consideration because it was
present both in liquid and gaseous product streams, which prevented its accurate quantification.

Ester conversion:

(x (t), %) = {(Nester, t = 0 − Nester, t = t )/Nester, t = 0 } · 100 (1)

Product selectivity:
(S(i), %) = {Nester, i /Nester tot. } · 100, (2)
where Nester, t = 0 stands for the initial number of methyl ester moles, Nester, t = t stands
for the number of methyl ester moles at reaction time t, Nester, i stands for the number
of methyl ester moles converted to product i, Nester tot. stands for the total number of
converted methyl ester moles.
All catalytic experiments were repeated 2–3 times to confirm their reproducibility, and
an experimental error was evaluated as ±5%.
In experiments with MeHe, turnover frequency (TOF) was calculated to evaluate the
specific activity of copper species in the catalysts with varying Cu/Zn using the equation:

TOF = (MMeHe · xMeHe) · (σCu ·NA /mcat ·SCu ), (3)

where MMeHe is the amount of MeHe loaded into reactor (mmol), xMeHe is MeHe con-
version, NA is Avogadro constant, mcat is the weight of a catalyst (g), and SCu is specific
copper area (m2 ·g−1 ), σCu is the cross-sectional area of copper equal to 0.0154 nm2 .
Catalysts 2021, 11, 1417 17 of 20

To follow changes in the characteristics of CuZn samples after catalytic tests, all spent
catalysts were separated from a reaction mixture by filtration, washed with acetone, and
dried at T = 60 ◦ C for 24 h. The produced spent samples were named as xCuZn-AR.
To understand the stability of the CuZn catalysts in repeated catalytic cycles, their
performance was evaluated in three consecutive reaction cycles. For this purpose, the
spent catalysts after a catalytic run were separated from the reaction mixture, washed
with acetone, dried in ambient temperature, and used in the next experiment without any
additional treatments. In this case, spent catalysts after the third catalytic run were named
as xCuZn-AR3.

4. Conclusions
The results presented in this study contribute to the understanding of the catalytic
performance of CuZn catalysts in the hydrogenolysis of carboxylic acid esters to corresponding
alcohols. First, experiments with catalysts differing in the Cu/Zn ratio of 0.5–6 confirmed
the positive function of ZnO species in stabilizing metallic copper particles and preventing
their sintering. Based on N2 O chemisorption and XRD results, it was suggested that the
initial activity of the catalysts in the conversion of methyl hexanoate was determined by
the surface area of copper particles and their size. As a consequence, the maximum initial
activity in the reaction was observed for a catalyst with the Cu/Zn ratio of 3. Nonetheless,
during the reaction, the performance of the catalysts changed, and a decrease in their
Cu/Zn ratio favored their stability in ester conversion. The high stability of catalysts
with the Cu/Zn ratio of 0.5 and 1 in the hydrogenolysis of esters was also confirmed by
experiments with three successive reaction cycles. The obtained results were explained
considering XRD results on the comparative evaluation of the size of Cu and ZnO particles
in calcined, reduced, and spent catalysts. Second, methyl hexanoate conversion resulted in
two main products: hexan-1-ol formed via the direct hydrogenolysis of the ester, and hexyl
hexanoate as the result of the transesterification reaction of methyl hexanoate with the
produced hexanol. Selectivity by transesterification reaction route unexpectedly increased
with a decrease in the content of ZnO particles, i.e., the active sites for this reaction step.
By correlating the obtained catalytic results with XRD and TPD data it was concluded
that the observed transesterification selectivity could be concerned with both the acid-base
properties of the CuZn catalysts and the size of the ZnO particles. Third, to explain the
excessive formation of the transesterification product, special experiments were carried
out on the conversion of either pure hexyl hexanoate and methyl hexanoate or their
mixtures. The obtained results demonstrated that the activity of CuZn catalysts in the
conversion of both esters was comparable. The accumulation of hexyl hexanoate among
the reaction products of methyl hexanoate hydrogenolysis could be explained by the
constant formation of the hexyl ester from the methyl ester and by the inhibiting the effect
of methyl hexanoate on hexyl hexanoate conversion. As a consequence, selectivity to
the latter product constantly increased with a growth in methyl hexanoate conversion,
and high selectivity to hexanol as a target reaction product could not be achieved until
methyl hexanoate conversion approached 100%. Finally, the investigated CuZn catalyst
showed a high efficiency in the conversion of methyl esters with the different lengths
of a carbon chain, varying from hexanoate to stearate. Only a slight decrease in the
conversion of a starting ester and an increase in alcohol selectivity (at the same conversion
level) were observed in the performed experiments, that could be explained by a steric
effect. The results obtained in this work can be used in forthcoming studies to optimize
the properties of copper-containing catalysts for the selective hydrogenolysis of esters to
corresponding alcohols.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/10

.3390/catal11111417/s1, Figure S1: The profiles of H2 consumption obtained for CuZn mixed oxides
with different Cu/Zn ratio, Figure S2: MeHe conversion observed during the conversion of MeHe +
1-Heol mixture in presence of reduced CuZn catalysts with different Cu/Zn ratio as well as single
Catalysts 2021, 11, 1417 18 of 20

phase ZnO and Cu catalysts, Figure S3: The comparison of Cu (A) and ZnO (B) particle size in spent
catalysts after the first (AR) and the third (AR-3) catalytic runs.
Author Contributions: Conceptualization, O.K. and D.K.; methodology, O.K.; investigation, O.K.,
J.A. and V.P.; data curation, O.K.; writing—original draft preparation, O.K.; writing—review and
editing, J.A., V.P. and D.K.; visualization, J.A. and V.P.; supervision, O.K.; project administration, D.K.;
funding acquisition, O.K. and D.K. All authors have read and agreed to the published version of
the manuscript.
Funding: Financial support from the Ministry of Education, Youth and Sport of the Czech Republic
is gratefully acknowledged (project No. LTACH19017).
Data Availability Statement: Not applicable.
Acknowledgments: TPD-CO2 and N2 O-RFC characterization results were obtained by using the
Large Research Infrastructure ENREGAT supported by the Ministry of Education, Youth and Sports
of the Czech Republic (project No. LM2018098). The authors are grateful to Jana Cibulková (UCT
Prague, Czech Republic) for XRD analyses, Simona Randáková (UCT Prague, Czech Republic) for
XRF analyses, Miloslav Lhotka (UCT Prague, Czech Republic) for N2 physisorption, and Dagmar
Fridrichová and Kateřina Karásková for TPD and N2 O chemisorption measurements (VSB-TUO,
Czech Republic).
Conflicts of Interest: The authors declare no conflict of interest.

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