Toward computational design of chemical reactions with reaction phase diagram

Abstract

Density functional theory (DFT) was rapidly developed and achieved a great success in the last decades. As the advancement of general concepts in heterogeneous catalysis, theoretical study of chemical reactions based on DFT calculations has become more and more feasible, which provides a guideline for the rational design of novel catalysts toward higher reaction activity and specific selectivity. Here, we review an innovate scheme, namely reaction phase diagram (RPD), which can offer not only an in-depth understanding of reaction mechanisms, but also the prediction of catalytic activity and selectivity trend over a collection of catalysts. The RPD analysis was successfully applied to understand the activity variation of CO 2 electroreduction to CO and formic acid, as well as thermochemical hydrogenation and dehydrogenation. Meanwhile, the RPD analysis also exhibits a success of studying the product selectivity in syngas conversion to methane, ethanol, and methanol with complicated reaction pathways. At the end, we review a successful case of catalyst rational design with a target of NO selective electroreduction to ammonia. The foundation of RPD analysis is based on the scaling relation of adsorption energies and the correlation between kinetic barriers and reaction energies at elementary steps. Therefore, microkinetic modeling is complementary to the RPD analysis. A few of limitations and the prospect of the development regarding the RPD analysis are addressed in this review. This article is categorized under:Structure and Mechanism > Reaction Mechanisms and Catalysisdensity functional theory, full pathway construction, global energy optimization, heterogeneous catalysis, reaction phase diagram | INTRODUCTIONHeterogeneous catalysis possesses a momentous value in many chemical processes, which has been widely focused in industry. Besides, it has been widely studied in academia, for example Fischer-Tropsch (FT) and ammonia synthesis, 1-3 selective catalytic reduction (SCR), CO oxidation, 4-5 CO 2 reduction reaction (CO 2 RR), and oxygen reduction reaction Chenxi Guo and Xiaoyan Fu contributed equally in this work.

Activity and Mechanism Mapping of Photocatalytic NO2 Conversion on the Anatase TiO2(101) Surface

“…The photogenerated charge may also give rise to a favored reaction pathway, which is different from the one under dark conditions. 35 Therefore, unveiling the mechanism of photochemical deNO 2 on TiO 2 surfaces is very important for improving catalyst design. In such a study, one should consider the full diversity of reaction pathways, but to date, mostly a few hypothetical and simplified reaction pathways were used only to study photocatalysis over oxides.…”

“…In principle, it is possible to develop a scheme with full consideration of all reaction pathways; however, the computational costs of the construction of extremely complex reaction networks is becoming the main challenge. Herein, we apply our recently developed new algorithm, 35 which allows considering the full set of pathways in an efficient way.…”

“…To analyze diverse reaction pathways, we applied a novel algorithm, as described in our previous work. 35 On the basis of experimental observations, we have considered two total deNO 2 reactions: 2NO 2 (g) + H 2 O(g) → HONO(g) + HNO 3 (g) and 2NO 2 (g) + 2H 2 O(g) → 2HONO(g) + H 2 O 2 (g). The 22 possible elementary steps considered are listed in Table S1.…”

“…More details of our algorithm were described in our previous work. 35 Under Dark Conditions. As shown in Figure 3a,b, it was found that all sites were selective to HONO + HNO 3 production under dark conditions, which is in agreement with the experimental report, 13 while the perfect surface exhibits the highest activity.…”

Autonomous Reaction Network Exploration in Homogeneous and Heterogeneous Catalysis

“…Many optimization and design strategies for more stable or active catalysts have been developed for specific fields such as biocatalysis [261][262][263][264][265][266][267][268][269][270], homogeneous catalysis [271][272][273][274][275][276][277][278][279][280][281], or heterogeneous catalysis [282][283][284][285][286][287][288]. In these strategies, the activity of a catalyst is judged on various physical descriptors.…”