Journal of Molecular Catalysis A: Chemical
Journal of Molecular Catalysis A: Chemical
Journal of Molecular Catalysis A: Chemical
a r t i c l e i n f o a b s t r a c t
Article history: This paper presents an overview of the evolution, advancements, and capabilities of the temporal anal-
Available online 26 June 2009 ysis of products (TAP) reactor system as a unique catalyst characterization tool. The origination of the
TAP reactor based on molecular beam scattering experiments is briefly mentioned. The advancement in
Keywords: TAP reactor design from the TAP-1 system to the TAP-3 system is introduced to highlight its relevance
Temporal analysis of products (TAP) as a valuable tool for elucidating mechanistic and kinetic aspects of adsorption, diffusion, and reaction
Heterogeneous catalysis
in gas–solid systems. Since the invention of the TAP reactor system, a series of TAP microreactor con-
Kinetics
figurations has been introduced with different amounts of catalyst packing starting from the one-zone
Transient methods
Gas–solid reactions
microreactor to the most recent introduction, the single particle microreactor in which a single Pt parti-
Knudsen diffusion cle is packed among 100,000 inert quartz particles. An advantage to decreasing the catalyst zone inside
Time-of-flight mass spectrometer the microreactor is to eliminate non-uniformity in the active zone while still achieving high conversions
Atomic beam deposition (95%). Experimental designs and results coupling the TAP reactor to other experimental systems such
Single particle experiments as a time-of-flight mass spectrometer and atomic beam deposition system is also presented. Key results
Pressure gap from recent TAP experiments are presented to show how the TAP reactor is used to answer fundamental
questions in catalysis such as bridging the pressure gap between industrial catalysis and surface science,
understanding the surface lifetimes of reactive adspecies in TAP pump-probe experiments, finding kinetic
rate constants related to changes in catalyst composition and its performance.
© 2009 Elsevier B.V. All rights reserved.
1. Introduction and chemicals when oil is no longer readily available is one of the
most challenging and important problems now facing humanity. An
Over the next several decades, a new generation of catalytic essential piece of the puzzle is the development of new approaches
materials and processes will be needed to meet the increasing to unravel the tangle of processes that occur on complex industrial
demands for fuel, food, chemicals, pharmaceuticals, and a whole catalysts.
host of materials (e.g., plastics and fibers). New catalysts will also Despite advances in surface science and computational chem-
play a pivotal role in environmental remediation and halting global istry that provide molecular level insight into surface physics and
warming. Currently, the petroleum-based process industry gen- chemistry, catalyst development for realistic processes still relies
erates products that have an annual worldwide production value extensively on empirical methods and trial and error processes.
exceeding 4 trillion dollars. Heterogeneous catalysis and multi- Generally the method used to develop practical catalysts follows
phase reaction engineering are the technology engines that power the catalyst development cycle (CDC) illustrated in Fig. 1. In the first
the chemical and fuel industries since nearly 75% of all chemicals, step of the CDC, candidate materials are selected to test as catalysts.
polymers, and advanced materials are produced with the aid of cat- In step two, the materials are synthesized, and in steps three and
alysts. In addition, over 90% of newly developed processes involve four, the materials are tested for catalytic activity, and characterized
catalysis, and over 95% of industrial reactors are based on heteroge- structurally.
neous catalytic processes. How to supply the vast quantities of fuels, The CDC includes a decision branch, which is reached through
steps three and four. This branch gives rise to a number of cyclic
paths. The path depicted by the red arrows represents a key cycle
in the CDC, and provides crucial performance information used to
∗ Corresponding author at: Department of Energy, Environmental, and Chemical
determine if the cycle can be exited. In practice, however, infor-
Engineering, Washington University in St. Louis, 1 Brookings Drive, St. Louis, MO
63130, USA. mation gained in a single cycle of the CDC often does not provide
E-mail address: gregoryyablonsky@yahoo.com (G. Yablonsky). guidance for the next step. In many cases, a cycle only provides
1381-1169/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2009.06.017
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 109
Nomenclature
tative of one specific catalyst state. Such changes can occur during micron size range. In addition to the crystalline phase or phases,
kinetic testing, and it is difficult to distinguish different catalyst catalysts may contain one or more amorphous phases deposited
states with most existing kinetic testing procedures. on the surface of the crystalline phases. The surfaces of the crystal-
According to the methodology of surface science, reactions are lites are composed of different crystal planes containing a variety of
carried out over a well-defined surface (e.g., a specific plane of a defects such as kinks, edges, steps, and vacancies. Defects may range
metal single crystal), so that the observed kinetics can be directly in size from microns to Angstroms (Å). The chemical composition
associated with the structure of the surface [5–8]. Surface science of a surface may be different from the underlying crystal bulk, and
techniques are used to define the structure of the crystal surface, can change under reaction conditions. In the case of metal oxides,
and to determine if a surface is changed by reaction. Information there is a lack of knowledge regarding surface reactions even on
pertaining to reaction-induced changes can be obtained by charac- well-defined surfaces [10]. In the case of “real” oxides, surface reac-
terizing a surface before and after reaction. Kinetics are obtained by tions at defect sites may dominate the chemistry, and these types
thermal desorption techniques or from scattering experiments. The of reactions are particularly difficult to study by surface science
kinetics often reflects the intrinsic reactivity of the specific crystal techniques.
plane being studied. By comparing the reactivities of different crys- Under reaction conditions, the kinetic state of a catalyst can
tal planes of the same metal, inferences can be drawn regarding the change. For example, the absolute number of active sites can change
nature of the active catalytic site. as a result of a change in the catalyst surface area, a change in the
Surface science techniques [5–8] can be used to characterize crystal morphology, or a change in surface oxidation state. During
the structure or composition of technical catalysts; however, direct reaction, the available number of active sites can change as a result
kinetic testing of technical catalysts in surface science systems is of adsorption. The specific reactivity of sites can change because
usually impractical. Structural and compositional data from surface the composition or structure of the sites changes. A process that
science experiments may be matched with data from atmospheric causes a change in the number of active sites may also cause a
pressure kinetics, but the heterogeneous surface structure of tech- change in structure of the active sites. In this case, the changes may
nical materials prevents the observed kinetics from being directly even compensate one another. Such effects complicate the prob-
associated with a specific crystal plane or surface structure. Also, lem of determining the number of active sites on a catalyst and
the structure of a technical catalyst may change when it is moved their specific reactivity. Consequently, to simplify the problem of
from atmospheric pressure conditions (esp. when the catalyst has determining the number of active sites and the kinetic characteris-
been exposed to a reactive mixture) to high vacuum conditions. tics of individual sites, the experimental strategy that is used should
In this case, the structural data may not be directly related to the provide a means of maintaining the catalyst in a constant state or
actual active site. should involve a change that is “insignificant”.
Experiments commonly used to obtain kinetic data at industrial Since Bennett and Kobayashi–Kobayashi times, it is well
reaction conditions are usually based on a steady-state approach. accepted in the heterogeneous catalysis literature that tran-
An important advantage of this approach is that it can be readily sient experiments can provide more mechanistic information
applied to technical catalysts. The steady-state approach has disad- about the reaction intermediates and pathways of the various
vantages, however, when it comes to developing activity–structure elementary steps when compared to steady-state experiments
relationships. First, steady-state kinetic data is usually related [11–13,155,164–167]. Steady-state kinetic experiments can reveal
to only the slow steps of a complex kinetic process, and does the performance of a catalyst after it has evolved into a stable
not provide detailed information. Second, the observed kinetics structure. Non-steady-state kinetic experiments reflect changes in
is a complex function of the gas-phase composition, the struc- performance that occur during the evolution process from one
ture/composition of the solid, and other process variables. As state to another state. The changes in kinetic properties can be
a result of these factors, details of the gas–solid reaction, and related to changes in catalyst composition and structure. However,
detailed activity–structure relationships, cannot be readily estab- non-steady-state experiments utilizing continuously stirred tank
lished using steady-state kinetic data. reactors have been plagued by a number of obstacles, e.g., macro-
The surface science approach provides a procedure for relating scale hydrodynamic non-uniformity in catalyst bed. In the Bennett
the surface structure of a solid to the reaction kinetics that occurs on review (1999) [167], it was concluded that “it is no longer advanta-
the solid surface. Consequently, surface science studies can provide geous to do these experiments in an ideal mixed-flow reactor”. See
activity–structure relationships. On the other hand, surface science a detailed analysis of this problem in [148].
experiments are performed at ultrahigh vacuum conditions using A new approach for characterizing the catalytic activity of tech-
well-defined model surfaces (e.g., metal single crystals), and are not nical and model catalysts called “interrogative kinetics” (IK) [14]
well suited for investigating kinetics on technical catalysts. combines vacuum pulse-response experiments, commonly known
A well-known problem that arises when attempting to compare as TAP experiments [14–16], with atmospheric pressure steady-
data from more practical studies with data from surface science state and transient experiments, and allows a single catalyst sample
studies is the so-called “pressure gap” problem first delineated [17,18] to be tested over a wide domain of pressures (105 –10−6 Pa)
by Bonzel [9]. He noted that the large difference in pressures and relaxation times (103 –10−4 s) [14,16]. The specific transport
(often greater than 9–10 orders-of-magnitude), and the difference domain in which kinetic data are obtained in TAP experiments
between single crystals versus technical catalysts makes it very dif- (Knudsen diffusion domain) is located on the boundary of the sur-
ficult to compare results from the two experimental regimes. In fact, face science domain. The approach is applicable to both model and
despite enormous strides in understanding how reactions occur on realistic catalysts, and provides a procedure for bridging the pres-
well-defined surfaces, large gaps exist in our fundamental under- sure gap [9].
standing of how reactions occur on “real” surfaces. Such surfaces The IK approach uses two types of experiments, called “state-
exhibit a complex multi-scale structure with critical dimensions defining” (SD) and “state-altering” (SA) experiments to probe
ranging from the microscopic to the atomic scale, and are not well different states of a catalyst sample. In a SD experiment, the catalyst
suited for study using ultrahigh vacuum surface science techniques. composition and structure change insignificantly during a kinetic
Many industrial catalyst particles are composed of metals test. In a SA experiment, the catalyst composition is changed in a
deposited on metal oxides or mixed-metal oxide microcrystallites controlled manner. The IK approach involves kinetic testing of a
bound together in a random orientation. A typical catalyst particle catalyst, and systematically altering its composition or structure
will contain a complex pore structure with pore dimensions in the in a well-defined process. For example, the oxygen composition of
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 111
2.1. Overview A basic TAP setup, depicted in Fig. 2(b), has some character-
istics common to an MBS experiment, and others common to
The Temporal Analysis of Products, or TAP experiment was con- conventional microreactor experiments. The key components are
ceived in the late 1970s to study catalytic reaction mechanisms on a “reaction zone” or microreactor, a fast-pulse gas feed system, a
industrial catalysts [14,16,19,20]. The initial thought was to devise a mass spectrometer detector, and a high-throughput ultrahigh vac-
simplified “molecular beam” experiment for multi-component cat- uum system. The reaction zone (Fig. 2), which holds the catalyst
alysts (e.g., mixed-metal oxides and supported metals) that have sample, is a temperature controlled cylindrical tube usually made
high surface areas and complex pore structures. Molecular beam of stainless steel, inconel, or quartz. One end of the tube receives
scattering (MBS) experiments [21–31] can provide fundamental input from the feed system, and the opposite end is open to vac-
information on surface structure, reaction dynamics, the elemen- uum. During an experiment the reaction zone and catalyst sample
tary steps of a reaction, and the kinetic parameters of individual are continuously evacuated. The reaction zone can hold practical
steps. When used in conjunction with surface characterization catalysts, which are commonly studied in conventional microreac-
techniques, data from a MBS experiment can establish the link tor experiments, as well as single particles, single crystals, or model
between kinetic properties and surface structure. On the other catalysts, which are studied in MBS experiments.
hand, MBS experiments use planar or decorated planar targets to MBS experiments obtain essential kinetic and mechanistic infor-
take advantage of the spatial characteristics of the beam. Industrial mation by modulating the reactant flux, and measuring the shift
catalysts have complex surfaces, are composed of multi-component in arrival times at the detector between scattered reactant and
mixtures of different metal oxides or metals combined with metal product molecules. The difference in arrival times can be used
oxides, and are generally not suitable for MBS experiments. The goal to determine reaction sequences, surface lifetimes of adspecies,
of early TAP designs was to retain the time-dependent features of a and rates of surface reactions. TAP pulse-response experiments
molecular beam experiment, minimize gas-phase interactions, and [14,16,19,20,32,33] extract kinetic information in a similar manner.
provide a way to extract intrinsic kinetic information from reac- Injection of a narrow gas pulse into the reaction zone initiates an
tions on bulk catalysts. The TAP experiment can be viewed as a experiment. The gas molecules travel through the reaction zone
bridge between MBS experiments and conventional microreactor where they encounter the catalyst and can react to form product
experiments. molecules. Molecules that exit the reaction zone are monitored
A variety of MBS setups have been described in the litera- by the mass spectrometer positioned at the outlet. An experi-
ture, and they generally fall into two different classes: (1) systems ment ends when the flow of reactant and product molecules is
designed to study gas-surface dynamics, and (2) systems designed no longer detected by the mass spectrometer. The observed char-
to study the kinetics and mechanism of surface reactions [6]. acteristic feature in a TAP experiment is the time-dependent gas
Fig. 2(a) presents a simplified diagram showing key compo- flow F(t) [moles/s] or [molecules/s] that escapes from the exit of
nents of a MBS apparatus. In a typical experiment a well-collimated the microreactor. The flow dependencies also have integral char-
beam of molecules having a known translational energy is directed acteristics that are related to the moments of the “flow-time”
toward a target surface, and the velocity and angle distributions dependencies [14,16,34]. Kinetic and mechanistic information is
112 J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134
obtained by analyzing these dependencies, and gas transport is At sufficiently small pulse intensities, a one-pulse TAP experi-
used as a “measuring stick” to determine the rates of chemical ment can be considered a state-defining experiment. The number
transformations. of molecules in a reactant pulse is typically much smaller (102 –105
In addition to kinetic and mechanistic information, TAP exper- times smaller) than the number of surface atoms in the catalyst
iments have been used to study transport processes in porous sample being probed [14]. As a result, the reactant pulse does not
materials, such as zeolites, and oxygen diffusion in metal and significantly perturb the catalyst surface.
metal oxide catalysts. The temperature dependence of TAP tran-
sient response curves provides intrinsic rate parameters that can be
2.4. TAP reactor applications
associated with the surface composition of a catalyst. The number
of active sites can be determined in TAP titration experiments.
Table 1 provides an overview of TAP reactor applications, and
the types of catalytic materials that have been studied including
2.3. Types of TAP experiments supported metals, mixed-metal oxides, zeolites, metal particles,
metals deposited on screens, catalytic monoliths, and nanoparti-
In both TAP and MBS experiments, the sample is maintained
cles or atoms deposited on microparticles, single crystals, and other
under vacuum conditions, which strongly promote desorption of
model catalysts.
adspecies. Prior to performing a TAP experiment, it is common to
heat the catalyst sample and monitor the desorption spectrum. Dur-
ing the heating process, adspecies (e.g., water, CO, CO2 , etc.), which 3. The TAP reactor system
cover the surface at ambient pressures, vacate the surface leav-
ing the coverage to more closely resemble that of an MBS target. The temporal analysis of products (TAP) reactor system was
Conversely, pulsing a specific species into the reaction zone can first patented by the Monsanto Company in 1986 as a novel
increase its coverage so that it resembles coverage at ambient pres- device for studying the kinetics and mechanisms of heterogeneous
sures. Pulsing different molecules in an alternating sequence can catalyzed gas-phase reactions by using a transient response tech-
adjust the surface coverage of two or more species. As a result, cov- nique with submillisecond time resolution [19]. Two years later
erage in a TAP experiment can be manipulated to resemble coverage in 1988, open literature publications by Monsanto catalyst scien-
in an MBS experiment or coverage in a conventional microreactor tists described how the TAP reactor system was used to elucidate
experiment. the mechanisms for several heterogeneous catalytic reactions hav-
The input pulse in a TAP experiment typically contains ≈1014 ing commercial significance [16,20]. Particular reactions that were
molecules, and the local pressure in an empty reaction zone may studied included n-butane oxidation to maleic anhydride over
reach ≈10−1 Pa during a pulse. If unimpeded, an oxygen molecule vanadium–phosphorus oxide (VPO) catalysts, propylene oxidation
can traverse the reaction zone in under 100 s. If the reaction zone to acrolein over bismuth–molybdates, methanol ammoxidation to
is filled with particles the pressure may reach ≈1.33 Pa in the void HCN over MnPOx and FeMoOx , and ethylene epoxidation over sil-
spaces if no adsorption occurs. The mean free path in an empty ver metal [95,96]. In 1989, Monsanto granted an exclusive license
reaction zone is about half the length of the reactor. In an empty to manufacture and sell a commercial version of the TAP reactor
reactor, molecules move in beam-like fashion and suffer relatively to Autoclave Engineers of Erie, PA. Later in that same year, DuPont
few collisions. In a packed reactor, the mean free path is ≈4000 m, became the first chemical company in the United States to purchase
which is significantly larger than the space between particles. As a a TAP reactor from Autoclave Engineers for the newly established
result, in a packed-bed reactor molecules collide with particles, but Corporate Catalysis Center in Central Research and Development
seldom with one another (Fig. 3). [20]. Later, the TAP-1 system was redesigned and simplified and
Fig. 3. Scale drawing of a TAP “reaction zone” and packed-bed microreactor containing a loading of nonporous spherical particles ≈250 m in diameter.
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 113
Table 1
Applications and theory of the TAP reactor including the corresponding catalytic materials tested.
Reactor transport (adsorption and diffusion) Zeolites, ␥-Al2 O3 , Rh/Al2 O3 , sulfated ZrO2 [35–42]
Environmental catalysis
N2 O abatement Pt, Pt-Rh mixed catalysts, Fe-MFI [74–78]
NOx storage Pt/BaO/Al2 O3 [79]
SCR of NOx Ag/Al2 O3 , Pt/ZSM-5, mordenite [80–82]
VOC U3 O8 [83]
Hydrogenation reactions
Acrolein hydrogenation Ag/SiO2 [84]
Oxidation reactions
Ammonia oxidation Pt, Pt–Rh mixed catalysts [85–89]
CO oxidation Au/Fe2 O3 , Au/Ti(OH)4 , La1−x Srx Fe(Pd)O3 , Pt, Pd/SiO2 [17,90–94,154,161,169]
Ethylene oxidation Ag powder [95,96]
o-Xylene oxidation VOx /TiO2 [97]
Propene oxidation Co10 Mo12 FeBiOx , ␥-bismuth molybdate [98–100]
Soot oxidation La3+ -doped CeO2 , CeO2 [101–103]
Toluene ammoxidation ␣-(NH4 )2 [(VO)3 (P2 O7 )]2 [104]
Toluene oxidation VOx /TiO2 , VOx /SiO2 [105–107]
eventually developed into the TAP-2 reactor system [14], which was The microreactor is positioned directly above the ionizer of the
commercialized by Mithra Technologies. The TAP-3 system retains mass spectrometer, and is attached to a movable stainless steel bel-
the basic design of the TAP-2, but is a fully automated instrument lows. A unique rotary-valve assembly is located between the ionizer
that can be operated either locally or remotely via the Internet. and the microreactor. It permits the microreactor to be operated at
vacuum conditions or atmospheric pressures, and allows the reac-
3.1. TAP apparatus design tor to be removed from the system without venting the vacuum
chambers. The reactor can be easily and rapidly switched from one
Fig. 4 presents a simplified schematic of a TAP-3 reactor sys- kinetic regime to another without exposing the catalyst sample to
tem, and Fig. 5 shows a photograph of a system. The TAP-3 reactor the atmosphere.
is comprised of (1) a pulse-valve manifold assembly that supplies When the rotary-valve is closed, the TAP microreactor can be
gas reactants for pulsed and flow experiments at user defined tem- operated as a continuous plug flow-type reactor at atmospheric
peratures and pressures, (2) a microreactor assembly that can be or higher pressures. In the “high-pressure” mode, the bulk of the
operated isothermally or in a temperature programmed mode, (3) a reactor effluent exits through an external vent. A small amount
mass spectrometer detector contained in a high-throughput ultra- can be leaked into the vacuum chamber through a variable leak
high vacuum system, and (4) a computer based control and data valve. The leaked material can be monitored with the mass spec-
acquisition system. trometer. In high-pressure experiments, the mass signal usually
The pulse-valve manifold contains one continuous flow valve changes relatively slowly, and can be collected in a scan mode.
and four high-speed pulse valves that are arranged to minimize In this mode, a complete mass spectrum can be acquired about
the dead volume between the valves and the microreactor. The once every 0.25 s. After performing an experiment at atmospheric
four pulse valves can be triggered simultaneously or in a pro- pressures, the microreactor can be quickly switched to vacuum con-
grammed alternating sequence. Pulse intervals can be varied from ditions by opening the rotary-valve.
microseconds to minutes. Switching between feeds is accom- With the rotary-valve in the open position, all of the reactor
plished electronically and can occur almost instantaneously. The effluent vents into the vacuum chamber. The movable bellows
continuous flow valve is connected to a separate manifold contain- allows the reactor outlet to be positioned within 2 mm of the ionizer
ing four flow controllers. The flow controllers and pulse valves can so that most of the effluent passes through the ionizer. As a result,
be operated simultaneously. very small inputs of gas can be detected, with a very high signal to
The TAP-3 vacuum system is comprised of two chambers sepa- noise (S/N) ratio (Fig. 6). The high S/N ratio allows accurate calcula-
rated by a pneumatically operated gate-valve, which is closed in the tion of the zeroth, first, and second moments of the response curves,
standby position. The lower chamber is evacuated by a 40 cm diam- and direct determination of many important kinetic characteris-
eter diffusion pump and associated mechanical pump. The chamber tics.
contains a cylindrical liquid nitrogen trap and adjustable baffle that For example, reactant conversion for a series of pulses can be
closes when data is not being acquired. The upper chamber holds determined from the zeroth moment. This change in conversion
the mass spectrometer and is pumped by a turbo molecular pump. can be related to a change in the concentration of the active cat-
The background pressure in the mass spectrometer chamber is typ- alytic species. The following quantities can be directly calculated
ically ≈10−7 Pa. from 0th, 1st, and 2nd moments: Conversion, selectivity, product
114 J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134
Fig. 4. Schematic of TAP-3 apparatus showing two-chamber vacuum system (base pressure = 10−7 Pa) with gate-valve, adjustable baffle, liquid nitrogen trap, rotary-valve for
switching between vacuum and pressure experiments, and quadrupole mass spectrometer; microreactor carousel with autoload microreactors and catalyst sample input
lines; reactant feed manifold with high speed pulse valves and continuous flow valve; gas feed system with heatable mass flow controllers, heated blend tanks for preparing
gas mixtures, and vacuum pump; computer control and data acquisition system indicating main control lines.
yield, residence time, apparent equilibrium and rate constants, and tions. Reactors are heated electrically and the reactor temperature
apparent time delay. controller provides an array of control options, which include con-
The TAP-3 system can accommodate microreactors of differ- stant temperature operation, programmed heating or cooling at
ent lengths (up to 25 cm) and diameters (up to 2 cm), which are a user defined rate, and the ability to perform multistep ramp-
useful for handling a variety of catalyst forms (see Fig. 7). A stan- soak programs. The standard microreactor can be heated to 800 ◦ C.
dard TAP microreactor is constructed of type 316 stainless steel Microreactors have also been fabricated from inconel and quartz
and can be operated at atmospheric pressures or at vacuum condi- which allow operation to temperatures as high as 1000 ◦ C.
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 115
Fig. 7. Examples of TAP packed-bed microreactor configurations and catalyst forms. See Fig. 22 for schematic of TAP system with pulse valves, slide valve, and mass
spectrometer.
116 J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134
optimize existing ones, often develop kinetic models based upon Reaction intermediates and products that have been reported
empirical power-law, classical Langmuir–Hinshelwood (LH), or in the catalyst literature when either n-butane, various butylenes,
Hougen–Watson (HW) rate expressions using kinetic data gen- or butadiene are used as the carbon source over various metal
erated from steady-state flow-type catalytic reactors, such as oxide catalysts include 1-butene, 2-butene, butadiene, acetone,
packed-bed microreactors [125]. Approaches based on mecha- methyl ethyl ketone, methyl vinyl ketone, furan, dihydrofuran,
nisms involve sequences of elementary steps where the precise maleic anhydride, acetic acid, crotonic acid, acrylic acid, glyoxylic
nature of catalyst active sites is not identified. These rate acid, methacrylic acid, formaldehyde, acetaldehyde, propionalde-
forms provide a well-known approach for fitting reaction kinetic hyde, crotonaldehyde, methacrolein, carbon oxides, and water
data, but do not provide a fundamental basis for design of [131]. Identification and quantification of the products gener-
new multi-functional catalyst materials using advanced princi- ated from these C4 hydrocarbons using steady-state and transient
ples of inorganic, solution-phase and computational chemistry response experiments poses a significant challenge for any on-
along with supporting advanced surface characterization meth- line analytical system because of the variety of reaction products
ods. Experimental reaction studies involving model compounds on that can exist under various reaction conditions and the common
well-characterized catalyst surfaces provide one alternate approach molecular functionalities between the various species. In the case
for developing insight in reaction mechanisms for these complex of packed-bed microreactor systems used for catalyst screening
systems. However, the absence of other key species in the reaction and kinetic evaluation for n-butane oxidation, such as the multi-
mixture can lead to various degrees of uncertainty in the applica- ple automated reactor system (MARS) [132–134], special-purpose
bility of model compound studies with idealized catalyst surfaces multi-dimensional gas chromatographic methods have been devel-
to the actual system. Transient response methods where all surface oped to resolve and identify all of the C1 to C4 hydrocarbons,
and gas-phase species are simultaneously monitored in real-time oxygen-containing organic species, and inorganic products [131].
provide a more robust approach for deciphering the kinetics and This suggests that special methods may be needed when perform-
mechanisms of these complex systems [126–130]. ing single ion monitoring of selected species to obtain reliable
Many examples can be cited from the literature where the transient response data for reacting systems involving a complex
products produced from gas-phase catalyzed reactions result in distribution of reaction products.
complex, multi-component mixtures containing a spectrum of both Fig. 9 is a matrix that shows typical molecules that have
organic and inorganic products. Two examples will be provided been identified in reaction mixtures for the partial oxidation of
here to illustrate some of the key challenges associated with mon- n-butane to maleic anhydride over vanadium–phosphorus oxide
itoring the transient responses of the gas-phase species using catalysts under oxygen-rich conditions as encountered in fixed-
quadrupole mass spectrometry, which is the primary analytical bed processes [135,141]. The organic products include acetic acid,
detector in the TAP reactor system. furan, dihydrofuran, acrylic acid, and maleic anhydride along with
Consider first the partial oxidation of various C4 hydrocarbons, various C4 hydrocarbons, COx , and H2 O. Selected ions produced
such as n-butane, iso-butane, iso-butylene, 1-butene, 2-butene, or from electron-impact ionization of each species are also listed
1,3-butadiene to various organic ethers, ketones, aldehydes, and to illustrate complexities that can occur if single-ion monitoring
carboxylic acids over various metal oxide catalysts. Fig. 8 shows is performed. Other ions are also produced but are not listed for
some of the reaction pathways and the associated products that can brevity. For a given hydrocarbon or organic oxygen-containing
be produced through the selective abstraction of hydrogen or the specie, several common ions occur so that the response for a
addition of oxygen to various starting reactants and reactive inter- particular ion would represent the combined response from
mediates. It is evident that a variety of isomers and other derivatives several species. Data handling methods for quantifying multiple
can be produced depending upon the dominant reaction pathway. ion responses that account for these effects are well-known in
Fig. 8. Reaction pathways and products that can be generated from the selective oxidation of various C4 hydrocarbons over metal oxide catalysts.
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 117
Fig. 9. List of species identified from GC/MS analysis of reaction products from the partial oxidation of n-butane over a vanadium–phosphorus oxide catalyst [134]. The
indicated ions for a given species are a subset of all the ions that can be generated to illustrate the overlap that can occur. The first row in the table indicates the mass to
charge ratio (m/z) of the species.
the mass spectrometry literature, which are often based upon these systems, and to briefly demonstrate their utility for studying
the implementation of convolution methods [136]. However, one heterogeneous catalysis behavior using the TAP reactor system.
complication that can occur when applying these to TAP data is that
transient experiments must be repeated at different ions before a 4.2. TAP reactor—time-of-flight system
composite set of ion response versus time data can be assembled.
This requires that the initial state of the catalyst can be reproduced This section summarizes the key results from a prototype sys-
within a tolerable level of error so that the resulting responses are tem that was developed to demonstrate the feasibility of coupling
representative of the same surface reactions that occurred in each a TAP reactor to a time-of-flight (TOF) mass spectrometer system
of the preceding set of experiments where the responses of differ- for simultaneous monitoring of multiple ions from a single pulse
ent ions were measured. This is particularly important for many or other type of input. A quadrupole mass spectrometer (QMS) was
catalysts where the surface coverage, oxidation state, active sites, also included in the system to provide an independent source of
etc. can undergo significant changes when exposed to small doses data for single ion monitoring.
of one or more species. Unless the composition of the reaction
products can be determined a priori through some independent 4.2.1. System description
means, such as GC/MS or from previous experience with the same A schematic of the prototype system that was developed to
catalyst system, caution must be exercised to ensure that the reso- test coupling of a TAP microreactor to a TOF mass spectrometer
lution and quantification of the primary reactants and products, i.e., is shown in Fig. 10. A simplified vacuum system was developed
n-butane, oxygen, maleic anhydride, carbon oxides, and water, is that allowed the TOF analytical package to be readily coupled to
not corrupted by the presence of one or more unidentified species. a TAP microreactor that was fitted with a set of high-speed pulse
Simultaneous measurement of both gas-phase and surface valves. Referring to Fig. 10, the system contains a single 20 cm vac-
species during the course of various TAP reactor transient response uum chamber in which the TAP fixed-bed microreactor and pulse
experiments for complex, multi-component catalytic reactions is valves are mounted in a vertical orientation in the center of the top
one of the outstanding opportunities associated with strengthen- plate. The microreactor and pulse-valve manifold are located on
ing, advancing, and broadening the utility of the technique. This the top of the vacuum chamber for ease of operation and mainte-
section summarizes some recent advances in coupling analytical nance. The reactor can be isolated from the primary chamber using
techniques to the TAP reactor as part of a larger effort to per- a custom-designed flange valve. A quadrupole mass spectrometer
form qualitative identification and quantitative analysis for the (UTI, Model 100C) is mounted on a 12 cm flange so the ionization
gas-phase species that are produced during the course of a single cage is perpendicular to the flight of the reactor product gas. This
transient response experiment. The particular methods described provides a secondary source of ion monitoring in addition to the
here include: (1) time-of-flight (TOF) mass spectrometry with TOF multiple ion monitoring comparison of the reactor responses.
electron-impact (EI) ionization, and (2) on-line gas chromatography A linear time-of-flight (TOF) mass spectrometer (Jordan TOF Prod-
with mass spectrometry (GC/MS) where gas samples are introduced ucts, Grass Valley, CA) is connected to the main vacuum chamber in
to the GC column by capturing a small (250 l) gas sample of the a horizontal orientation using a six-inch flange. The flight tube has
transient response at various times along the response trajectory. an overall length of ca. 91 cm that terminates with a microchan-
The primary objective here is to illustrate the basic features for nel plate (MCP) detector. The electron gun for the TOF system is
118 J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134
mounted on a 7 cm flange directly across from the flight tube grid electron-impact ionization, is illustrated in Fig. 11. The basic princi-
assembly. To monitor the pressure in main vacuum chamber and ples and operation of the TOF are generally described by Cotter [137]
the flight tube, full-range ion gauges are mounted on two 2 cm so they are omitted here. The molecular beam generated from the
flanges. Vacuum in the primary chamber is provided by a 520 l/s TAP is introduced to the ionization zone which initiates the various
turbo molecular pump, while additional vacuum for the TOF flight processes needed to create a product signal from the microchannel
tube is provided by a 210 l/s turbo molecular pump. With this com- plate detector (MCP). The design shown in Fig. 11 is a linear TOF,
bination of pumps, a background pressure of ca. 10−6 Pa is achieved although the current version in our lab employs an angular reflec-
in the flight tube, while 10−5 Pa is obtained in the primary chamber. tron (AREF) TOF for higher mass resolution. Because the TOF system
The fixed-bed TAP microreactor is constructed of type 316 stain- was being evaluated for the first time as a new technique for collec-
less steel and has an inner diameter of 5.5 mm with an overall tion of time-resolved transient kinetic data from a heterogeneous
length of 41.7 mm. It seals against the heated valve manifold using a catalyzed reaction, a special-purpose control and data acquisition
Kalrez® O-ring (DuPont Performance Elastomers, Wilmington, DE). system was developed using commercially available components.
A custom-designed splitter valve for directing a continuous con- The TOF spectrometer is typically calibrated by injecting a gas
trolled leak of the reactor product gas to the vacuum chamber can mixture containing He, Ne, N2 , Ar, and CO2 , Xe, and other compo-
also be attached to the reactor exit. The reactor is packed by sand- nents using the TAP reactor pulse-valve manifold and measuring
wiching the catalyst particles between two sections of 250–425 m the time-of-flight of the detected ions. These gases are selected
quartz beads. The front inert section serves to preheat the inlet to span the range of molecular weights that are typically encoun-
gas, while the post-inert section minimizes the dead volume and tered in TAP reactor applications, such as those involving the partial
broadening of the response once the product gas exits the catalytic oxidation of light hydrocarbons. The flight time for CO2 is about
section. 10 s so that a complete product gas mass spectrum for typical gas-
phase heterogeneous reactions can be typically collected in about
4.2.2. TOF operation and data collection 30–40 s. By contrast, the time required for the UTI quadrupole to
The basic design concept of the TOF spectrometer, when used scan over the same range, assuming 4 points per amu, would be a
as a detector for TAP reactor transient response experiment with few seconds. The TOF clearly permits rapid detection of multiple
Fig. 11. Linear time-of-flight mass spectrometer. VA1 = repeller plate voltage, VA2 = extraction grid voltage, VFOC = focusing voltage, VX1 = beam steering voltage and
MCP = microchannel plate detector.
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 119
Fig. 12. Comparison of experimental and model-predicted responses obtained when the TAP–TOF system is operated using the QMS and TOF detectors. (a) QMS detector;
pulsed gas = He; packing = SiC granules; particle density p = 3.2 g/cc; particle diameter dp = 175 m; reactor inner diameter dr = 5.5 mm; T = 25 ◦ C; packing length L = 10 mm
(case 1) and 40 mm (case 2). (b) TOF detector; pulsed gas = CO2 ; packing = quartz granules; particle density p = 2.6 g/cc; particle diameter dp = 338 m; reactor inner diameter
dr = 5.5 mm; T = 25 ◦ C; packing length L = 40 mm.
ions from a single pulse input at a rate that is several orders-of- sion is the primary mode of gas transport and instrument effects
magnitude faster when compared to the QMS. are negligible.
Fig. 14. Chromatogram from FID analysis of a product mixture from a typical steady-
state catalyst test for the partial oxidation of 1,3-butadiene to furan. Reactor feed
composition: 8.8% 1,3-butadiene, 10.3% oxygen, 9.0% nitrogen and balance: helium;
reaction temperature: 380 ◦ C. GC column: 0.53 mm i.d. × 30 m 1701 phase, film thick-
ness = 5 m.
5.1. Basic concepts of reaction. This process has been demonstrated using the selective
oxidation of hydrocarbons over a transition metal oxide catalyst
There are three basic concepts that form the basis for extracting (e.g., vanadyl pyrophosphate or VPO) [33,140]. An oxidized VPO
kinetic information from TAP Knudsen pulse-response experi- sample was exposed to a series of hydrocarbon pulses and the
ments: change in kinetic properties were determined as a function of the
oxidation degree.
1. Well-defined Knudsen diffusion is a “measuring stick” for mea-
suring chemical reaction rates and extracting kinetic parameters. 5.1.4. TAP studies and model-free kinetic analysis
2. During a single pulse experiment the solid catalyst changes The goal of model-free kinetic analysis is to obtain the rate
insignificantly and controlled change occurs in a multi-pulse of chemical transformation without assuming a specific kinetic
experiment. model. Temkin and Denbigh applied a model-free approach to the
3. The solid catalyst surface composition will remain uniform if the analysis of steady-state kinetics for over 50 years. In their approach,
active zone is a sufficiently small fraction of the total bed length. the rate of chemical substance transformation is equal to the dif-
ference between the inlet and outlet molar flow rates divided by
The first and second concepts were reported implicitly in the the catalyst volume or surface area. In CSTR steady-state experi-
first TAP paper in 1988 [16]. In the 1997 TAP paper [14], the above ments no assumptions regarding the type of kinetic dependence,
concepts were expressed explicitly and presented mathematically. the reaction mechanism, or the corresponding model are needed to
The concept of uniformity was stressed in the paper devoted to the determine the rate of chemical transformation. Model-free kinetic
thin-zone TAP reactor in 1999 [109]. analysis of non-steady-state reactions [148] is a recent develop-
ment that began with the TZTR microreactor configuration.
5.1.1. Knudsen diffusion as a “measuring stick” A model-free kinetic method known as the “Y-procedure” [148]
Since Temkin’s [143–145] and Denbigh’s [146,147] times, a com- has been used to extract the non-steady-state rate of chemical
mon approach for extracting kinetic information is to measure the transformation from reaction-diffusion data with no assumptions
rate of chemical reaction using the rate of mass transport as a regarding the kinetic model. This method will be briefly described
“measuring stick.” In traditional steady-state experiments with per- in a separate section of this paper. The Y-procedure consists of the
fect mixing, convectional transport is the “measuring stick” and following steps:
diffusional transport is neglected. In TAP Knudsen pulse-response
experiments there is no convective flow and Knudsen diffusion is 1. Exact solution in the Laplace domain.
the only gas transport process. In the absence of reaction, the gas 2. Switching to the Fourier domain to allow sufficient computation.
exit flow from the microreactor is described by a standard diffusion 3. Introduction of discretization and filtering in the Fourier domain
curve. In the “reaction-diffusion” case, the exit flow response curve to deal with real data (in the time domain) subject to noise.
is different from the standard diffusion curve, and this difference is
attributed to reaction. Overall, the methodology used in TAP Knudsen pulse-
response experiments combines experimental conditions that
5.1.2. Insignificant change in the solid catalyst during single pulse simplify the physico-chemical system with basic mathematical
experiment and controlled change during multi-pulse experiments ideas—especially with the idea of infinitesimal change.
When the number of reactant gas molecules in a single pulse is
significantly smaller than the number of catalytically active sites on 5.2. One-zone TAP microreactor
the catalyst, the catalytic system remains in essentially the same
state after the measurement. This type of experiment is called a In the one-zone microreactor model the total reactor volume is
“state-defining” experiment [14]. A series of state-defining exper- uniformly packed with catalyst particles. The one-zone model and
iments can cause the catalyst state to change, and the change its mathematical framework were introduced in the first TAP paper
is characterized by the amount of consumed/released gaseous published in 1988 [16]. The mathematical model is based on the
substances. A series of state-defining experiments is termed a following assumptions:
“state-altering” experiment [14].
1. The fractional voidage of the catalyst bed is constant.
5.1.3. Uniformity of the catalyst surface composition across the 2. There is no radial concentration gradient in the catalyst zone.
active zone 3. There is no radial or axial temperature gradient in the catalyst
When a heterogeneous catalyst is exposed to a reactant gas the zone.
composition and kinetic properties of the catalyst can change as a 4. There is no intra-particle or surface diffusion.
result of reaction with the gas. In a packed-bed reactor, the gas flow 5. The diffusivity of each gas is constant and independent of the
can cause the change to occur non-uniformly. The inlet of the bed composition of the mixture as a whole.
will see the highest reactant concentration, and will change by the
largest amount. In a non-steady-state experiment the bed compo- The last assumption results from using an evacuated microreac-
sition can also change in time. An important and unique feature of tor and small pulse intensities, which guarantees the validity of the
a TAP pulse-response experiment is that the catalyst composition Knudsen diffusion regime. The mass balance equations for a num-
remains essentially uniform when the thickness of the catalyst zone ber of important gas transport and transport-kinetics interactions
is small compared to the total length of the packed bed. In practice a in the one-zone reactor are presented below.
small amount of catalyst can be packed in a “thin zone” between two
beds of inert particles or in some cases a single particle can be used. 5.2.1. Diffusion only
The advantage and properties of a thin-zone TAP reactor (TZTR) In a packed-bed reactor, the mass balance equation for Knudsen
have been discussed in detail in the literature [33,109–112,148]. The diffusion of a non-reacting gas A (e.g., neon, argon and krypton) is
properties of a single particle TAP reactor [17,18] have recently been given by
described.
Using a TZTR, a catalyst sample can be characterized “state-by- ∂CA ∂2 CA
εb = DeA , (1)
state” to determine how its catalytic properties change as a result ∂t ∂z 2
122 J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134
The initial condition, Eq. (2), specifies that at t = 0, the gas con-
centration at the reactor inlet can be represented by the delta
function. Boundary condition one, Eq. (3), specifies that the input
flux is zero at the microreactor entrance when the pulse-valve is
closed. Boundary condition two, Eq. (4), specifies that the gas con-
centration at the microreactor outlet is very close to zero. This
condition results from the continuous evacuation of the microre-
actor outlet by the vacuum system. The diffusivity term in the
Knudsen diffusion regime is determined by the following equation
[32]:
ε d 8RT 4εb
De = b i , di = rp . (5)
3 M 3(1 − εb )
Eq. (8) describes the dimensionless exit flow rate as a function and
of dimensionless time. The resulting curve (Fig. 16) is known as
DeA
the standard diffusion curve. For any TAP vacuum pulse-response Hp = 1.85 . (13)
experiment that involves only gas transport, the standard diffusion εb L2
curve should be the same regardless of the gas, microreactor bed By multiplying Eq. (10) with (11) and Eq. (12) with (13) gives a
length, catalyst particle size, or reactor temperature. The area under relationship between the time at which the peak maximum occurs
the standard diffusion curve is to equal unity. In dimensional form, on a standard diffusion curve and its corresponding peak height.
Eq. (8) can be rewritten as This calculation can be used to verify that gas transport through
the reactor is Knudsen diffusion:
DeA
∞
FA tDeA
= (−1)n (2n + 1) exp(−(n + 0.5)2 2 ). (9) F̄A,p p = tp Hp ≈ 0.31. (14)
NpA εb L2 εb L2
n=0
5.2.2. Diffusion + irreversible adsorption/reaction
Eq. (9) indicates that the pulse shape of the curve generated in
If adsorption or reaction is first order in gas concentration, and
a diffusion only experiment should be independent of the pulse
surface coverage is negligible (the result of small pulse intensity)
intensity if the gas molecules are transported through the microre-
compared to the total amount of active catalytic material, then the
actor in the Knudsen diffusion regime.
mass balance for the gas-phase component A is given by Eq. (15):
A unique feature of the standard diffusion curve is the time, p ,
at which the curve maximum occurs is given by ∂CA ∂2 CA
εb = DeA − as Sv (1 − εb )ka CA , (15)
1 ∂ ∂z 2
p = , (10)
6 which can also be written in dimensionless form:
and the corresponding height of the peak maximum is given by ∂C̄A ∂2 C̄A as Sv (1 − εb )ka L2
= − k̄a C̄A , k̄a = . (16)
∂ ∂ 2 DeA
F̄A,p = 1.85. (11)
The dimensionless exit flow rate for irreversible adsorption or
Eqs. (10) and (11) can be rewritten in dimensional form in terms reaction combined with Knudsen diffusion process is given by
of time and height as
∞
Fig. 18. Comparison of standard diffusion and diffusion + reversible adsorption exit-
Fig. 17. Comparison of diffusion + irreversible adsorption/reaction exit-flow curves
flow curves. (a) Standard diffusion exit-flow curve, k̄a = 0, (b) diffusion + reversible
with the standard diffusion curve. (a) Standard diffusion exit-flow curve, k̄a =
adsorption curve, k̄a = 20, k̄d = 20 and (c) diffusion + reversible adsorption curve,
0, (b) diffusion + irreversible adsorption/reaction curve, k̄a = 3 and (c) diffu-
k̄a = 20, k̄d = 5[14].
sion + irreversible adsorption/reaction curve, k̄a = 10.
Fig. 22. Illustration of high-pressure (a), and vacuum (b) configurations of TAP reactor system. The microreactor can be shifted from high-pressure operation to vacuum in
minutes by opening the slide valve.
introduced through the continuous valve, giving a gas residence and then decreased at the same ramp rate to room temperature.
time in the reactor of 1.8 s. A small amount of the reactor effluent was diverted into the mass
The temperature dependence of CO2 production was obtained spectrometer chamber, and its mass spectrum was continuously
by heating or cooling the reactor at a constant rate while maintain- monitored.
ing an input flow of 50 cc/min. The internal reactor temperature Both TAP vacuum and atmospheric flow data exhibit a turning
was ramped from 40 to 430 ◦ C over a 40 min interval. Upon reach- point in CO2 production indicating a transition from reaction con-
ing 430 ◦ C, the reactor temperature was held constant for 5 min trolled by one adsorbed species to one controlled by a different
Fig. 23. (a) Schematic of TAP single particle microreactor configuration. The 400 m diameter Pt particle is packed within a sea of inert quartz particles with diameters
between 210 and 250 m. (b) Image comparing a 400 m Pt particle to a pencil point. (c) SEM image showing the complex surface structure of a polycrystalline Pt particle.
(d) Higher magnification (15,000×) of the particle shown in (c), which shows the surface is non-porous [17].
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 127
Fig. 24. Illustration of a TAP pump-probe experiment in which O2 /Ar and CO2 /Ar are pulsed in an alternating sequence and the CO2 transient response is measured during
each pulse.
adsorbed species at 170 ◦ C. The upper branch in the CO2 curve of ments can be used to describe kinetic behavior in the atmospheric
the atmospheric flow experiment corresponds to an O2 covered sur- pressure domain.
face, and the lower branch corresponds to a CO covered Pt surface Taking the conversion of CO or the CO2 yield at the “turning
(Fig. 25(b)). From the pulse response data, in the region of the CO2 point” from vacuum pulse response and atmospheric flow data, the
maximum, the areas under the CO2 response curves (CO2 yield) cor- apparent kinetic rate constant can be calculated. In combination
responding to the O2 and CO pulses are approximately the same, with the gas residence time () in the catalyst zone, the apparent
indicating nearly equal coverages of O2 and CO (Fig. 25(c)). The kinetic rate constant is given by the following expression:
correspondence in “turning points” indicates that the coverage in
vacuum and atmospheric pressure experiments is approximately X
kapparent = . (40)
the same and the intrinsic kinetic data obtained in vacuum experi- (1 − X)
Fig. 25. Comparison of CO2 produced during TAP vacuum pump-probe experiments and atmospheric flow experiments for CO oxidation over single Pt particle with the
same composition of reactants. (a) A typical set of pump-probe CO2 responses (m/e = 44) for reaction at 140, 170, and 350 ◦ C. There is a shift in the amount of CO2 produced
during both CO and oxygen pulses as temperature increases. (b) CO2 production observed from atmospheric flow experiment. The CO2 produced while increasing reactor
temperature is less than the CO2 produced during reactor temperature decrease as shown by the counter-clockwise hysteresis loop. (c) CO2 production observed from vacuum
pump-probe experiment. The black line represents the total CO2 yield. The red and blue lines represent the CO2 yield on the oxygen pulse and CO pulse, respectively. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.)
128 J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134
Fig. 26. (a) Oxygen uptake over reactor-equilibrated VPO at 105 Pa O2 and (b) O2 desorption spectrum under vacuum from 18 O2 -treated (VO)2 P2 O7 .
Using an approximate conversion of 90% in the vacuum VOPO4 phases [56–60]. The oxidation of n-butane, and other C4
pulse-response experiment, the apparent kinetic rate constant is compounds was investigated in TAP pulse-response experiments
calculated to be 9000 s−1 . In the atmospheric flow experiment, by pulsing a C4 /Ar mixture over VPO and measuring the pulse
using a conversion of 20% the apparent kinetic rate constant is response curves of the reactants and products. Fig. 27 shows typical
calculated to be 9280 s−1 . The two apparent constants differ by response curves and an Arrhenius plot for n-butane oxidation over
approximately 3%. Although there may be some error involved in an oxygen-treated catalyst.
experimentation, the values of the apparent kinetic rate constants The change in kinetic parameters as the surface oxygen con-
are approximately the same. The ability to relate data both qual- centration is altered is shown in Fig. 28, which plots the activation
itatively and quantitatively in the atmospheric pressure domain energy and apparent equilibrium constant for different products
to the data obtained in vacuum pulse-response experiments using at different stages in the reduction of VPO. The mechanistic impli-
a single Pt particle is a step toward bridging across the pressure
gap.
Fig. 29. Schematic of atomic beam deposition system coupled to a TAP-2 reactor system [94].
port process, the temperature, and gas–solid interactions. It is oping structure–activity relationships. Constructing a detailed
standard practice to use an inert gas (typically argon) as an inter- mechanism requires knowledge of the different species (reactants,
nal reference. At reaction temperatures, the total time inert gas surface complexes, catalyst components, desorbing intermediates,
molecules spend interacting with the solid is negligible, and the and products) participating in the overall reaction, and the time
inert gas response can be assumed to be solely a function of the gas
transport process and temperature. Under Knudsen flow conditions
an inert gas response is described by the “standard diffusion curve”
(see Section 5.2.1). The standard diffusion curve for any gas with
a unique molecular weight at any temperature can be constructed
from the inert gas response. Deviation from the standard diffusion
curve is evidence of a gas–solid interaction.
Catalytic reaction mechanisms represent the sequence of
molecular level processes that occur during a single catalytic cycle.
Processes typically included in a mechanism are reactant adsorp-
tion and desorption, surface diffusion, surface reaction, and product
desorption and re-adsorption. The mechanism may also include
structural and compositional changes that occur in the catalyst.
Experimental data on such changes are very useful for devel-
Fig. 31. Pump-probe data showing CO2 production as a function of temperature and
pump-probe interval. At 150 ◦ C the CO2 production is essentially independent of the
Fig. 30. Normalized CO2 production (determined by measuring the zeroth moment pump-probe interval out to 9 s separation. At 350 ◦ C the CO2 production drops as the
of the CO2 responses) over fresh Pd deposits (750 pulses) obtained by pulsing CO pump-probe interval increases indicating a drop in the active oxygen concentration
and ramping the reactor temperature from 32 to 400 ◦ C [94]. with time.
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 131
7.1.3. Multi-pulse TAP experiments and discriminated using these expressions. In the case of the
TAP experiments usually involve a series of single or alternat- global-transfer matrix approach, the general theory of the pulse-
ing pulses containing fixed concentrations of reactants and inert response–pulse experiment for the multi-zone configuration has
reference gas. A single reactant can be used to produce a con- been described. The theory offers an efficient means to compute
trolled change in the catalyst surface composition. For example, the actual profiles of gas and surface concentration in the reac-
CO, hydrogen, or a hydrocarbon can be pulsed over a mixed-metal tor as well as the corresponding values at the reactor exit using
oxide to deplete the surface oxygen, and change the oxidation state the fast Fourier transform. For the thin-zone TAP reactor (TZTR) in
of surface metal ions. At the same time the transient responses of which the gas and catalyst composition are nearly uniform, the the-
reactants and products over the course of the reduction can be used oretical expressions are very simplified (see Section 5.4 [109,112]).
to monitor changes in reaction products and in catalytic properties. In this case, every substance can be characterized by three appar-
Reduction of a mixed-metal oxide strongly influences its adsorption ent parameters obtained using three observed moments, i.e., the
properties, and can cause a change in the reaction mechanism. Com- apparent kinetic constant, the time delay, and ‘equilibrium con-
parison of changes in catalytic properties with changes in surface stant’ [33,163]. These expressions have been used for developing
composition provides information to develop activity–structure or a new strategy for kinetic characterization of states in a TAP reac-
activity–composition relationships, and to construct models of the tor with multi-pulse responses that is called “state-by-state-kinetic
active catalytic site. screening”. This strategy was illustrated using furan oxidation
TAP multipulse experiments using a TAP-2 reactor system with over a VPO catalyst [33]. Essential information on the apparent
three-zone and thin-zone microreactor configurations were used parameters as a function of the catalyst oxidation/reduction degree
to investigate the dependence of kinetic parameters for hydrocar- and comparative analysis of these parameters create a basis for
bon oxidation on VPO catalysts as a function of the oxygen surface developing a detailed reaction mechanism. For example, calcula-
concentration [170,171]. Typical experimental results are shown tions demonstrate that apparent kinetic constants for all products
in Figs. 27 and 28 in Section 6.2.1. Catalysts were initially heated (maleic anhydride, acrolein, and CO2 ) are clearly different at all oxi-
in an oxygen atmosphere, and the oxygen uptake was measured dation/reduction degrees. Thus, the reaction routes for all products
as a function of temperature and O2 partial pressure. Oxygen was should be distinguishable. The non-linear dependence of apparent
readily adsorbed at temperatures above 400 ◦ C, in amounts total- kinetic constants on the oxidation degree is explained by assuming
ing 1–3 monolayers (see Fig. 26). The resulting “oxygen-treated” a reaction with participation of catalyst oxygen, particularly sub-
catalyst was then reduced with a hydrocarbon (e.g., n-butane, surface oxygen. Time delays for all mentioned products are clearly
butene, butadiene and furan) in series of anaerobic pulses at dif- distinguished as well, and the number of distinguished time delays
ferent temperatures (see Fig. 27a). Arrhenius plots obtained from indicates the number of surface intermediates. The proposed mech-
the pulse response data for different VPO oxidation states is plotted anism must include at least three independent routes involving at
in Figs. 27b and 28a. The data shows that the number of active sites least four surface intermediates.
or active oxygen species decreases as the catalyst is reduced and Recently, a new procedure, the so-called Y-procedure [148], was
the activation energy for n-butane conversion increases. The con- developed for determining the gas concentration and reaction rate
version increases suddenly without a significant decrease in the in the active zone of the thin-zone TAP reactor (TZTR) without mak-
surface oxygen concentration indicating the reaction shifts to a dif- ing any assumptions on the detailed mechanism and corresponding
ferent active site (active oxygen species). The rapid change can be kinetic dependence. Hence, the method is essentially independent
explained as follows: energy of activation changes linearly with the of the kinetic model. The mathematical basis of this procedure is
change in surface composition and therefore, the kinetic constant a Laplace-domain analysis of two inert zones in a TZTR followed
and conversion change exponentially with the composition as well. by transposition to the Fourier-transform domain. When combined
Similar experiments were performed with other hydrocarbons, and with time discretization and filtering, the Y-procedure leads to an
it was found that both the product spectrum and kinetic parame- efficient and practical method for reconstructing the kinetic depen-
ters (Fig. 28b) were a strong function of the hydrocarbon reactant dences in the catalyst zone. It also can be considered as a basis for
and the VPO oxidation state. During butane oxidation experiments advanced software for non-steady-state kinetic data interpretation
it was found that reaction intermediates such as butene, butadiene, and detail mechanism development.
and furan formed and desorbed at lower surface oxygen concentra- In summary, a variety of mathematical techniques have been
tions, their production at higher surface oxygen concentrations was developed for parameter estimation from theoretical models of the
suppressed. transport-kinetics interactions that occur in the TAP reactor using
pulse response data. Some of these are traditional methods that
7.2. Quantitative information on mechanisms have a well-established history in the transient response literature
for catalytic systems. Newer tools that recognize the unique oper-
Models that describe the transport-kinetic processes that typi- ating features of the TAP reactor, such as the “Y-procedure”, have
cally occur in TAP pulse-response experiments are parabolic partial also been developed and provide a simple yet robust approach for
differential equations (see Section 5). Typically, the model parame- extracting fundamental kinetic and other surface-related parame-
ters are extracted from the pulse response data by using parameter ters. It is expected that the increased development of new software
estimation methods. A review of different methods for parameter tools for solution of partial differential equations as well as user
estimation from TAP pulse response data was recently presented by interfaces will lead to a new generation of methods that allow
Schuurman [162]. Different approaches based on analytical solu- robust analysis to be performed using a large range of TAP pulse
tions have been developed during the last decade and include the response data sets.
moment-based approach [32–34] and the global-transfer matrix
approach [118,119,123,124]. 8. Summary
The moment-based approach is well established and com-
pares the analytical expressions for the zeroth, first and second The TAP reactor system provides the catalyst scientist with a
moments of the model-based pulse response to the moments that unique capability to unravel the chemistry, kinetics, and mecha-
are evaluated from the TAP response data. Parameters such as the nisms of gas–solid catalyzed reactions using a variety of transient
effective diffusivity and kinetic constants can be obtained. Dif- response protocols. These protocols and the associated knowledge
ferent mechanisms and corresponding models can be compared have been developed over a period of 20+ years, and are based
J.T. Gleaves et al. / Journal of Molecular Catalysis A: Chemical 315 (2010) 108–134 133
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