Topological analysis of catalytic reaction networks: Water gas shift reaction on Cu(111)

Callaghan, Caitlin; Vilekar, Saurabh A.; Fishtik, Ilie; Datta, Ravindra

doi:10.1016/j.apcata.2008.05.004

Cited by 44 publications

(31 citation statements)

References 43 publications

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“…[2,3] By using a microkinetic model, Schumacher et al [4] suggested that Cu and Ni may be promising as superior catalytic components for WGS catalysts. This conclusion was supported by Callaghan et al [5] through reaction-route graph analysis and Zeigarnik et al [6] who used the unity bond index-quadratic exponential potential (UBI-QEP) method. It is well-known that water dissociation is generally recognized as the rate-limiting step for the entire WGS process and Ni is more reactive toward H 2 O dissociation than Cu.…”

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confidence: 76%

Do Ni/Cu and Cu/Ni Alloys have Different Catalytic Performances towards Water‐Gas Shift? A Density Functional Theory Investigation

et al. 2014

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Density functional calculations were preformed to investigate whether adding Ni into a Cu surface (denoted as Cu/Ni) or adding Cu into a Ni surface (Ni/Cu) is more efficient for catalyzing the water-gas shift (WGS)? The reactions of water dissociation and monoxide dissociation were selected to assess the activity and selectivity towards WGS, respectively. Our results show that Ni-atom modification of surfaces is thermodynamically favorable for both reactions. Kinetically, compared with pure Cu, water dissociation is greatly facilitated on Ni-modified surfaces, and the activity is insensitive to the Ni concentration; however, monoxide dissociation is not well-promoted on one Ni-atom-modified surfaces, but two Ni-atom modification can notably decrease the dissociation barriers. Overall, on the basis of these results, we conclude that 1) the catalytic performance of bimetallic metals is superior to monometallic ones; 2) at the same Ni concentration on the surface, Cu/Ni and Ni/Cu alloys have almost the same performance towards WGS; and 3) to acquire high WGS performance, the surface Ni atoms should either be low in concentration or highly dispersed.

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confidence: 76%

Do Ni/Cu and Cu/Ni Alloys have Different Catalytic Performances towards Water‐Gas Shift? A Density Functional Theory Investigation

et al. 2014

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“…We will follow the example of the WGS reaction, which we have analyzed before via the RR graph approach, 44 but using a recent DFT microkinetic model for the Pt-Re(111) catalyst. 58 This system with a single OR is not only of great practical significance in a variety of processes but also is one in which the microkinetic models developed are of significant, although not overwhelming, complexity, so that our RR graph-based paring approach can be illustrated meaningfully and without excessive complexity.…”

Section: Resultsmentioning

confidence: 99%

“…These can, in fact, be determined simply from an inspection of the mechanism, thus avoiding the step of systematic stoichiometric algorithm as described in our earlier publications. [41][42][43][44]56,57 Such an independent set for this mechanism is provided in Table 2. In fact, the complete set of FRs and ERs can subsequently be determined topologically as walks, once the RR Graph is constructed.…”

Section: Constructing the Rr Graphmentioning

confidence: 99%

“…3,7,39,40 However, it is a "black box" numerical approach. Here, we discuss an alternate approach based on electrical network analogy of a reaction mechanism within the reaction route (RR) graph analysis approach [41][42][43][44] developed by us, which involves an evaluation of the reaction step "affinity," or driving force, and "resistance" under a variety of conditions. It is just as rigorous and substantially more revealing than Campbell's DRC, allowing transparent pruning of complex catalytic reaction networks.…”

Section: Introductionmentioning

confidence: 99%

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Ockham's razor for paring microkinetic mechanisms: Electrical analogy vs.Campbell's degree of rate control

2015

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Elucidation of the key molecular steps and pathways in an overall reaction is of central importance in developing a better understanding of catalysis. Campbell's degree of rate control (DRC) is the leading methodology currently available for identifying the germane steps and key intermediates in a catalytic mechanism. We contrast Campbell's DRC to our alternate new approach involving an analysis and comparison of the "resistance" and de Donder "affinity," that is, the driving force, of the various steps and pathways in a mechanism, in a direct analogy to electrical networks. We show that our approach is as just rigorous and more insightful than Campbell's DRC. It clearly illuminates the bottleneck steps within a pathway and allows one to readily discriminate among competing pathways. The example used for a comparison of these two methodologies is a DFT study of the water-gas shift reaction on Pt-Re catalyst published recently.

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“…Microkinetic modeling has been applied in the past for a variety of chemical processes such as methane partial oxidation and reforming [14,57,58], selective catalytic reduction of NO x [59,60], NO oxidation [61], ammonia decomposition [13,62], ethylene hydrogenation [63], and Water-Gas Shift [64][65][66], to name a few recent applications.…”

Section: Chapter 3: Surface Reaction Mechanism Developmentmentioning

confidence: 99%

Microkinetic modeling and analysis of ethanol partial oxidation and reforming reaction pathways on platinum at short contact times

Koehle

Mhadeshwar

2012

Chemical Engineering Science

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2013iii ACKNOWLDGEMENTSThere are many people without whom this thesis would not have been possible. I must thank Ashish Mhadeshwar for the incredible amount of knowledge he imparted and the guidance he provided in order for this research to be conducted, shared at conferences and published. Many thanks to Doug Cooper, Bill Mustain and Ranjan Srivastava for standing in as advisors and providing support that was above and beyond expectations. I want to thank everyone that has become part of my UConn family, without whom this project would have been possible but much less fun:

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Topological analysis of catalytic reaction networks: Water gas shift reaction on Cu(111)

Cited by 44 publications

References 43 publications

Do Ni/Cu and Cu/Ni Alloys have Different Catalytic Performances towards Water‐Gas Shift? A Density Functional Theory Investigation

Do Ni/Cu and Cu/Ni Alloys have Different Catalytic Performances towards Water‐Gas Shift? A Density Functional Theory Investigation

Ockham's razor for paring microkinetic mechanisms: Electrical analogy vs.Campbell's degree of rate control

Microkinetic modeling and analysis of ethanol partial oxidation and reforming reaction pathways on platinum at short contact times

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