Chemistry of Inorganic Materials 1 (2023) 100004

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Chemistry of Inorganic Materials

journal homepage: www.elsevier.com/locate/cinorg

Layered double hydroxides derived CuFe-based catalysts for CO2

hydrogenation to long-chain hydrocarbons
Ju Huang, Zhiyuan Zhang, Yuxue Wei *, Lisheng Guo, Jiuyi Liu, Chenghua Zhang, Zhaoming Xue,
Song Sun
School of Chemistry and Chemical Engineering, Anhui University, Hefei, 230601, Anhui Province, China

A R T I C L E I N F O A B S T R A C T

Keywords: CO2 hydrogenation to yield long-chain hydrocarbons has attracted tremendous attention in both academic and
CO2 hydrogenation industrial field. CuFe-based bimetal catalysts have been widely applied in CO2 hydrogenation owing to their low
Layered double hydroxides cost, facile preparation, and excellent performance. In this study, a series of CuFe-based catalysts with different
CuFe-Based catalyst
Cu/Fe molar ratios have been synthesized from layered double hydroxide precursor. The optimized CuFe8-LDO
catalyst with Cu:Fe¼1:8 exhibits a C5þ selectivity of 45% at CO2 conversion of 9.5%. Through systematic char-
acterizations including TEM, TPR, TPD, XPS, it is revealed the abundant and highly dispersed CuO favors the
reduction of iron species, and enhances CO adsorption capacity of as-prepared catalysts. This study provides an in-
deep understanding of Cu on CO2 hydrogenation performance of Fe-based catalysts.

1. Introduction anions [13–16]. Even after high-temperature calcination, the atomically

dispersed metals in LDH are maintained [17,18]. In this work, a series of
Over the past few decades, excessive CO2 emission has caused various ternary CuFe-based catalysts were synthesized from LDH precursor for
environmental problems, such as global warming and ocean acidification CO2 hydrogenation.
[1,2]. CO2 capture and utilization (CCU) is a promising strategy to
simultaneously reduce excessive CO2 concentrations and convert this 2. Experimental
greenhouse gas into high value-added chemicals [3,4]. Among them,
catalytic hydrogenation of CO2 has received enormous attention in both 2.1. Materials
academic and industrial field. Iron based catalysts have been widely
utilized in CO2 hydrogenation, in which CO2 are firstly reduced to CO via Analytical grade chemicals including Fe(NO3).39H2O, Cu(NO3).23H2O,
reverse water-gas shift (RWGS) reaction and then CO are converted into Mg(NO3).26H2O, NaOH and Na2CO3, of which Na2CO3 comes from
hydrocarbons through Fischer-Tropsch synthesis (FTS) process [5,6]. Tianjin Damao Chemical Reagent Factory, and the rest come from
However, it is difficult for a catalyst with single-component to simulta- Sinopharm Chemical Reagent Co., Ltd.
neously fulfill the aforementioned two steps. In this regard, catalysts with
multi-components have been explored, in which Cu has been widely used 2.2. Synthesis of catalysts
in catalyst preparation [7–9]. Cu can not only improve the reduction of
Fe, but also serve as active phase for RWGS reaction to increase the CO In a typical synthesis, solution A was prepared by dissolving 0.02 mol
partial pressure, and thus, the overall CO2 hydrogenation activity of Fe(NO3).39H2O and 0.06 mol Mg(NO3).26H2O in 100 mL deionized water.
Fe-based catalysts are enhanced [10–12]. It is worth noting conventional Solution B was obtained by dissolving certain NaOH and Na2CO3 in 100
impregnation and co-precipitation methods to synthesize CuFe-based mL deionized water. Solution A and solution B were simultaneously
catalysts usually generate uneven distribution of active phases, which dropped into a beaker containing 50 mL deionized water at 60  C under
are prone to easy sintering and agglomeration. stirring, and pH were maintained at 8.8. Then the formed slurry was
Layered double hydroxides (LDH) are composed of positively charged transferred into Teflon-coated stainless steel autoclave and maintained at
(M2þ, M3þ)(OH)6 octahedral layers and negatively charged interlayer 110  C for 5 h. The obtained precipitates were filtered and washed with

* Corresponding author.
E-mail address: weiyuxue@ahu.edu.cn (Y. Wei).

https://doi.org/10.1016/j.cinorg.2023.100004
Received 29 December 2022; Received in revised form 27 March 2023; Accepted 1 May 2023
Available online xxxx
2949-7469/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
J. Huang et al. Chemistry of Inorganic Materials 1 (2023) 100004

LDH. The molar amount of Fe3þ and Mg2þ is kept constant, by adding
different amount of Cu2þ, the molar ratio of Cu2þ and Fe3þ were kept at
1:16, 1:8, 1:4, 1:2 respectively, labelled as CuFe16-LDH, CuFe8-LDH,
CuFe4-LDH and CuFe2-LDH.
The LDH precursors were then calcined at 700  C for 4 h with a
heating rate of 2  C/min. The obtained layered double oxides (LDO)
catalysts were named as Fe-LDO, CuFe16-LDO, CuFe8-LDO, CuFe4-LDO,
and CuFe2-LDO.

2.3. Catalytic testing

CO2 hydrogenation were carried out in a fixed bed reactor. 0.2 g LDO
catalyst mixed with 0.2 g quartz sand were placed at the constant tem-
perature zone. The catalysts were firstly reduced at 400  C for 6 h under
100 mL/min hydrogen flow. After reduction, the reaction was took place
at 300  C, 3 MPa, H2:CO2¼3, and GHSV¼6000 mL.g-1.h-1. The gaseous
products were analyzed online by gas chromatography (GC) and liquid
products were collected in cold trap for offline GC analysis. The yield of
C5þ hydrocarbons was calculated as followed:

Yield(C5þ)¼Conv.(CO2)*Sel.(C5þ)*[1-Sel.(CO)]

2.4. Characterization

X-ray diffraction (XRD) patterns were recorded using a SmartLab 9

kW X-ray diffractometer with Cu Kα radiation. Scanning electron mi-
croscopy (SEM) was performed on a Regulus 8230 scanning electron
microscope at an acceleration voltage of 5 kV. Transmission electron
microscopy (TEM) and high-resolution transmission electron microscopy
(HRTEM) images were conducted on a field-emission electron micro-
scope (JEM-2100F, Japan). Atomic force microscopy (AFM) was per-
formed on AFM 5500 M. The textural properties of catalysts were
analyzed by N2 adsorption-desorption conducted on Model Belsorp Max
instrument (BEL Japan, Inc.) at 77 K. H2 temperature-programmed
reduction (H2-TPR), CO2 and CO temperature-programmed desorption
(CO2-TPD, CO-TPD) were performed on Micromeritics Auto Chem II
2920. The surface elements and electronic states of samples were
Fig. 1. XRD patterns of (a) LDH precursors, and (b) LDO catalysts. analyzed using X-ray photoelectron spectroscopy (XPS, Escalab 250Xi).

deionized water several times until pH¼7, and then dried in a vacuum
drying oven at 80  C for 12 h. The obtained precursor was named as Fe-

Fig. 2. SEM images of LDH precursors (a) Fe-LDH, (b) CuFe16-LDH, (c) CuFe8-LDH, (d) CuFe4-LDH, (e) CuFe2-LDH.

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J. Huang et al. Chemistry of Inorganic Materials 1 (2023) 100004

Fig. 3. SEM images of LDO catalysts (a) Fe-LDO, (b) CuFe16-LDO, (c) CuFe8-LDO, (d) CuFe4-LDO, (e) CuFe2-LDO.

3. Results and discussion 45-0937) located at 2θ¼35.5 and 38.7 are only observed in CuFe2-LDO
catalyst, which might be associated with the high dispersion of Cu species
3.1. Characterization of catalysts [22–24].
The SEM images of LDH precursors are given in Fig. 2. It is found the
The XRD patterns of Fe-LDH precursor and CuFe-LDH precursors are LDH precursors exhibit thin sheet-like morphology with size of 150–300
shown in Fig. 1a. Both Fe-LDH precursor and CuFe-LDH precursors nm. Fig. S1 shows the SEM images and corresponding elemental mapping
exhibit characteristic diffraction peaks at 2θ¼11.3 , 22.7 , 34.1 , 38.5 , of as-prepared LDH precursors. It can be seen Fe, Mg and Cu elements are
45.7 , 59.4 , 60.6 , which correspond to the (003), (006), (012), (015), uniformly distributed on the LDH precursors. Compared with Fe-LDH,
(018), (110) and (113) plane of hydrotalcite, respectively [19]. In the uniform distribution of Cu in CuFe-LDH demonstrates that the Cu
addition, the magnesium carbonate and magnesium hydroxide diffrac- has been successfully doped into the LDH structure. This further confirms
tion peaks are observed, which can be attributed to the emission of Mg2þ the successful synthesis of CuFe-LDH. SEM images of obtained LDO cat-
during hydrothermal process [20]. After calcination at 700  C, the XRD alysts via calcination of LDH precursors are shown in Fig. 3. Even after
patterns of derived LDO catalysts are given in Fig. 1b. The disappearance high-temperature calcination, the thin sheet-like morphology of initial
of hydrotalcite structure and the diffraction peaks of mixed oxides are LDH remain unchanged [25,26]. However, the CuFe4-LDO catalyst ex-
detected. The diffraction peaks at 2θ¼30.1 and 35.5 correspond to the hibits certain stacked granules. The CuFe2-LDO catalyst shows an obvious
(220) and (311) of MgFe2O4 spinel phase (JCPDS 88-1943). The irregularly stacked granular morphology with few nanosheets. The par-
diffraction reflections at 2θ¼42.9 and 62.3 correspond to the (200) and ticle size distributions (PSD) of Fe-LDO, CuFe4-LDO and CuFe2-LDO
(220) of MgO phase (JCPDS 78-0430) [21]. As can be seen, all of the LDO catalysts are given in Fig. S2. The average size of Fe-LDO nanosheets is
catalysts exhibit the diffraction peaks of MgO and MgFe2O4 phase. It 178 nm. With the addition of Cu, the average size of CuFe4-LDO and
should be noted the characteristic diffraction peaks of CuO (JCPDS CuFe2-LDO nanosheets decreases to 139 and 76 nm, respectively. Atomic

Fig. 4. (a, b) TEM and (c, d) HRTEM images of CuFe8-LDO.

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J. Huang et al. Chemistry of Inorganic Materials 1 (2023) 100004

Fig. 6. H2-TPR profiles of the LDO catalysts.

seen CuFe8-LDO exhibits obvious fringe spacing corresponding to (110)

and (311) crystal planes of MgO and MgFe2O4, which is consistent with
XRD results.
In order to examine the specific surface area and pore structure of
LDO catalysts, N2 adsorption-desorption isotherms were performed, as
shown in Fig. 5. All samples exhibit typical type IV isotherm, indicating
micropores are presented in the catalysts [29]. The BET specific surface
area, pore volume and average pore diameter of catalysts are shown in
Table 1. Obviously, the BET specific surface area, pore volume and
average pore size of LDO catalysts decline with the addition of Cu. This
may be due to the destructive sheet-like structure of the LDO catalysts
induced by Cu [30].
In order to investigate the effect of Cu/Fe molar ratio on the reduction
ability of LDO catalysts, the H2-TPR profiles of the LDO catalysts are
shown in Fig. 6. In the H2-TPR of Fe-LDO catalyst, two reduction peaks
Fig. 5. (a) N2 adsorption-desorption isotherms, and (b) pore size distribution are observed. The first reduction peak appears at 442  C, which corre-
curves of LDO catalysts. sponds to the reduction of Fe2O3 to Fe3O4 in MgFe2O4. The second
reduction peak appears at 530  C, corresponding to the reduction of
Fe3O4 to metallic iron [31,32]. With the addition of Cu, a new reduction
Table 1 peak appears at 197  C, which corresponds to the reduction peak of the
Texture properties of the LDO catalysts. highly dispersed CuO species. Meanwhile, the reduction peaks of Fe
Catalyst SBET (m2 g1) Vtotal (cm3 g1) Average pore diameter (nm) species in the CuFe16-LDO catalyst decrease to 420  C and 520  C,
Fe-LDO 39.60 0.09 9.34
respectively, indicating that the addition of Cu facilitates the reduction of
CuFe16-LDO 39.45 0.06 6.25 Fe species in the catalyst. The CuFe8-LDO exhibits the lowest reduction
CuFe8-LDO 22.76 0.03 5.35 temperature. Further increasing the amount of Cu, two reduction peaks
CuFe4-LDO 18.40 0.02 5.38 of Cu species appear between 200 and 300  C and the peak area gradually
CuFe2-LDO 15.00 0.02 5.48
increases. This is due to the increase in the number of CuO and oligo-
meric CuO species on the catalyst surface [33]. This is consistent with the
force microscopy (AFM) has been widely used to measure the thickness detection of CuO diffraction peaks in the XRD pattern of CuFe2-LDO. At
and lateral dimension of samples. As shown in Fig. S3, the thickness of the same time, the reduction peaks of Fe species shift to a high temper-
Fe-LDO and CuFe4-LDO nanosheets is 24 and 25 nm, respectively, while ature, indicating that the highly dispersed CuO species is more favorable
that of CuFe2-LDO catalyst is 56 nm. It is obvious the thickness of for the reduction of Fe species. With the increase of Cu/Fe molar ratio,
CuFe2-LDO catalyst is much larger than that of Fe-LDO and CuFe4-LDO the reduction temperature of the catalyst first increases and then de-
catalysts. Regarding the reason for the change in the morphology of LDO creases. The improved reduction behavior is conducive to the formation
catalysts, it is believed that the Jahn-Teller effect of Cu ions leads to a of iron carbides.
decrease in the thermal stability of LDH precursors [27,28]. After the The proper basicity of the catalyst is beneficial for the conversion of
introduction of excessive Cu, the inevitable Jahn-Teller effect results in CO2 into long-chain hydrocarbons. According to previous studies, the
the structural collapse of the CuFe4-LDO and CuFe2-LDO catalysts after adsorption strength of CO2 on the catalyst can be classified into weak
calcination. Fig. S4 shows the elemental mapping of the LDO catalysts, adsorption (90-149  C), medium adsorption (150-400  C) and strong
from which we can see the Fe, Mg and Cu elements are uniformly adsorption (400-600  C), corresponding to the initial adsorption of CO2,
distributed without obvious agglomeration. It is reasonable the highly CO2 activation and C–C coupling reaction, respectively [34]. Fig. 7a
dispersed CuFe-based catalysts can be obtained from LDH precursors via shows the CO2-TPD profiles of LDO catalysts. The Fe-LDO catalyst shows
calcination. a strong adsorption peak of CO2. With the addition of Cu, weak adsorp-
TEM images of CuFe8-LDO catalyst are presented in Fig. 4. It can be tion peaks are observed in CuFe8-LDO and CuFe16-LDO catalysts,

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J. Huang et al. Chemistry of Inorganic Materials 1 (2023) 100004

Fig. 9. CO2 conversion, CO selectivity and product selectivity over Fe-LDO and
CuFe-LDO catalysts.

temperature is significantly enhanced after the addition of Cu. The

enhanced high temperature CO adsorption peak is not only beneficial to
reducing the CO selectivity, but also to improve the C5þ yield and CO2
conversion. Similar to CO2-TPD, excessive Cu inhibits the adsorption of
CO on the catalysts.
Fig. 8a shows the Cu 2p XPS spectra of CuFe8-LDO. Two satellite
peaks appear at 938.8–947 eV and 959-965 eV, indicating that the Cu
species on the catalyst surface exist in the form of CuO. The Mg 1s XPS
spectra of Fe-LDO and CuFe8-LDO samples are shown in Fig. 8b. The
binding energy of Mg 1s in the Fe-LDO sample locates at 1303.6 eV.
Compared with Fe-LDO sample, the Mg 1s peak in CuFe8-LDO shifts to
lower binding energy, which can be ascribed to the CuO incorporation
[35].

Fig. 7. (a) CO2-TPD profiles, and (b) CO-TPD profiles of the LDO catalysts. 3.2. CO2 hydrogenation activity

accompanied with strong adsorption peak. Further increasing the The catalytic performance of the Fe-LDO and CuFe-LDO catalysts is
amount of Cu, the intensity of the medium adsorption of CuFe4-LDO and shown in Fig. 9. The high CO selectivity of Fe-LDO may be due to the
CuFe2-LDO catalysts increases, while that of the strong adsorption peak strong RWGS reactivity of LDH-derived spinel catalysts. With the in-
decreases. At the same time, the amount of CO2 adsorbed by the catalysts crease of Cu/Fe molar ratio, the CO2 conversion increases gradually from
decreases, which may be related to the decrease in specific surface area. 5.8% of Fe-LDO catalyst to 15.7% of CuFe2-LDO catalyst, and the CO
The adsorption of reaction intermediates on catalysts is also impor- selectivity decreased from 84% of Fe-LDO catalyst to 38% of CuFe2-LDO
tant. Fig. 7b shows the CO-TPD profiles of LDO catalysts. In the Fe-LDO catalyst. The hydrocarbon selectivity is also affected by the Cu/Fe molar
catalyst, two CO adsorption peaks appear in the temperature range of ratio. With the increase of Cu/Fe ratio, the C5þ selectivity of LDO cata-
150–300  C and 400-550  C, respectively. The adsorption peak at high lysts shows a volcanic trend. It increase from 12.9% of Fe-LDO catalyst to
43% of CuFe8-LDO catalyst and then decreased to 20.3% of CuFe2-LDO

Fig. 8. XPS spectra of (a) Cu 2p of CuFe8-LDO sample, and (b) Mg 1s of Fe-LDO and CuFe8-LDO samples.

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