文献类型：期刊文献

英文题名：Co-enhanced Pd-based catalysts for direct synthesis of hydrogen peroxide: Insights from DFT studies and experimental verification

作者：Jiang, Donghai Shi, Yongyong Zhou, Liming Ma, Jun Yin, Chaochuang Lin, Qian Pan, Hongyan

第一作者：Jiang, Donghai;蒋东海

通信作者：Lin, Q[1];Pan, HY[1]

机构：[1]Guizhou Univ, Sch Chem & Chem Engn, Guiyang 550025, Guizhou, Peoples R China;[2]Guizhou Univ, State Key Lab Publ Big Data, Guiyang 550025, Guizhou, Peoples R China;[3]Guizhou Key Lab Green Chem & Clean Energy Technol, Guiyang 550025, Guizhou, Peoples R China;[4]Guizhou Inst Technol, Sch Chem Engn, Guiyang 550003, Guizhou, Peoples R China;[5]Liupanshui Normal Univ, Sch Chem & Mat Engn, Liupanshui 553004, Guizhou, Peoples R China

第一机构：Guizhou Univ, Sch Chem & Chem Engn, Guiyang 550025, Guizhou, Peoples R China

通信机构：corresponding author), Guizhou Univ, Sch Chem & Chem Engn, Guiyang 550025, Guizhou, Peoples R China.

年份：2024

卷号：1002

外文期刊名：JOURNAL OF ALLOYS AND COMPOUNDS

收录：;EI(收录号：20242516295242);Scopus(收录号：2-s2.0-85196414796);WOS:【SCI-EXPANDED(收录号:WOS:001259612100001)】；

基金：Thanks for the computing support of the State Key Laboratory of Public Big Data, Guizhou University. This work was financially supported by National Natural Science Foundation of China (Grant No. 22068009) , National Natural Science Foundation of China (Grant No. 22262006) , Guizhou Provincial Science and Technology Projects (Grant No. QKHJC-ZK [2022] YB088) , and Guizhou Provincial Basic Research Program (Natural Science) ( [2022] 534) .

语种：英文

外文关键词：Cobalt modification; Pd-based catalyst; Supported catalyst; Direct synthesis of H2O2; Electronic structure

摘要：Direct synthesis of hydrogen peroxide (H2O2; DSHP) from hydrogen and oxygen is a highly promising method for H2O2 production. Herein, we propose a novel optimization strategy that uses cobalt (Co) to regulate the electronic structure of Pd, thereby enhancing the catalytic performance of the DSHP. Density functional theory (DFT) studies indicate that the introduction of Co increases the activation energy for O-2 dissociation and decreases the hydrogenation activation energy, thereby promoting H2O2 generation. The experimental results demonstrate that Co considerably enhances the catalytic activity of Pd by modulating the Pd lattice strain and surface Pd-0/Pd2+ ratios. Specifically, the optimized Pd-Co-5/NPCs exhibit outstanding catalytic performance, with H2O2 selectivity and productivity reaching 72.4 % and 306.8 mol/Kg(cat)(-1)h(-1), respectively, which are considerably superior to those of traditional Pd/NPC catalysts. Further in-depth DFT calculations reveal the regulatory mechanism of Co on Pd's electronic structure in the DSHP. Co induces electron transfer and compressive stress in Pd, leading to a richer electron state in Pd and a lowered d-band center, thereby benefiting the catalytic process. Comodified Pd-based catalysts reduce the hydrogenation activation energies of O-2* and OOH* and increase their dissociation activation energies, thereby improving H2O2 selectivity and productivity. In addition, CoO loaded on the Pd/Co(111) surface forms hydrogen bonds with OOH* and HOOH*, thereby altering the H2O2 synthesis performance. This research enhances our understanding of the role of transition metals and their oxides in catalytic performance during DSHP, providing new insights into the design and development of high-performance catalysts.