Descriptor Design in the Computational Screening of Ni-Based Catalysts with Balanced Activity and Stability for Dry Reforming of Methane Reaction

Abstract

Dry reforming of methane (DRM) is an important reaction in the actual environmental and energy crisis context. It enables the production of syngas from CO 2 and CH 4 reforming. While Ni catalyst presents a high activity regarding this process, it often suffers from deactivation. It was found that the Sn-doped Ni catalyst can avoid carbon deposition, but a decrease in DRM reactivity was also observed. In this work, we used density functional theory calculations in combination with microkinetic modeling first to understand how Sn doping affects the resistance to carbon deposition and the surface catalytic activities of Ni. Based on the understandings, we found that an ideal dopant should give rise to a proper adsorption energy of carbon such that (i) the C* formation process, e.g., CH 4 dissociation, is rate-controlling to improve the carbon resistance and (ii) relatively low dissociation barriers of CH 4 and CO 2 can be achieved to maintain a good activity. Therefore, the adsorption energy of carbon and the dissociation barriers of CH 4 and CO 2 can be utilized as descriptors for the stability and activity of Ni-based catalysts. Subsequently, we screened several metal dopants and found that the descriptors designed are capable of providing a consistent activity and stability trend with experiments reported in the literature. Therefore, our work could provide relevant guidelines to rationally design efficient catalysts for the DRM reaction.

Comparative evaluation of Ni‐based bimetallic catalysts for dry reforming of methane at low temperature: The effect of alloy itself on performance

“…Ni‐Pd/Al 2 O 3 has lower activity than that of Ni/Al 2 O 3 despite the lowest activation energy barrier for feed gas conversion. According to Chen and coworkers, if the energy barrier for CH 4 decomposition is less than that for CO 2 dissociation, the catalytic resistance to carbon coking would decrease 56 . In DRM, the formation of C* on the catalyst surface originates from CH 4 decomposition, and oxygen species that oxidize adsorbed carbon comes from CO 2 dissociation.…”

DFT-based microkinetic model analysis of dry reforming of methane over Ru7/CeO2(111) and Ru7/CeO2(110): key role of surface lattice oxygen vacancy

“…The catalysis microkinetic analysis package (CatMAP), [42][43][44] which is a powerful and flexible powerful package, was researched by Nørskov's group to study the microkinetic modeling by utilizing descriptor-based analysis. CatMAP as a formidable tool has been used extensively to study the trends across various catalysts.…”

Promotional Effect of Ni−Sn Interaction over Ni Supported on Sn‐incorporated MCM‐41 Catalysts for CO2 Reforming of CH4

“…found that combining DFT with microkinetic modelling approach, the Sn‐doped Ni catalysts surface with weak adsorption strength of carbon increased the resistance of coke deposition compared with the pristine Ni. However, the lower affinity of carbon caused an improvement in the dissociation barrier of CH 4 and CO 2 , the DRM activity was decreased at the same time [19] . Additionally, the reducibility and basicity properties of Sn species also have significant influences on the catalytic performance [16] …”