文献类型：期刊文献

英文题名：General Rules of Coverage-Affected Activity Trends and a Widened Optimal Adsorption Energy Zone in Locating the Catalyst

作者：Lai, Zhuangzhuang[1,2];Xia, Jie[1,2];Jia, Menglei[1,2];Chen, Jianfu[1,2];Wang, Haifeng[1,2]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China

年份：2024

卷号：128

期号：25

起止页码：10421

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20242516273802);WOS:【SCI-EXPANDED(收录号:WOS:001245131800001)】；

基金：This project was supported by National Key R&D Program of China (2021YFA1500700), NSFC (22203031, 91945302, 92045303, and 21703067), National Ten Thousand Talent Program for Young Top-notch Talents in China, and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Adsorption - Catalyst activity

摘要：The non-Langmuirian nature of a catalyst surface caused by the adsorbate-adsorbate interactions generally results in an activity gap between the theoretical evaluation and experimental measurement. However, a general theory to understand this is still lacking and the optimal activity window has yet to be identified. Here, three typical coverage-dependent adsorption energy variation behaviors, including linear, logarithmic, and Z-type functions (where the adsorption energy initially remains stable and then rapidly decreases to a plateau), are quantitatively investigated in terms of how they influence the activity trend using a two-step catalytic model. Compared to the conventional volcano-shaped curve without coverage effect, the coverage-affected activity curve generally shows a broadened peak area and activity upshift on the left side of the volcano curve, while the right side remains little changed. The broadened peak area indicates that more catalysts than expected can exhibit excellent catalytic activity under the realistic conditions. More importantly, we reveal that the width of the broadened peak area is mainly determined by the adsorption energy difference affected by the coverage from 0 to 1 ML (named as the maximum coverage error) and is almost independent of the types of coverage effects, while its threshold can be directly identified by the half principle we proposed earlier (E-I(o,opt) approximate to (mu(R) + mu(P) )/2). Quantitatively, the activity increase on the left side correlates with the transition-state structure type of product dissociation and the maximum coverage error. Following these rules, a strategy for quickly sketching the coverage-affected activity curve is discussed. These findings have important implications for catalyst design and make it convenient to quantitatively assess the experimental activity.