Electronic regulation & improved conductivity of molecular catalysts as electrocatalysts

Hu, Bihua1,2; Cao, Hailin3; Lei, Zhiwei1; Cui, Shuyu1; Wang, Peizhi1; Tang, Jun2; Wang, Xingzhu1,4; Xu, Baomin1

2024-07-01

10.1039/d4cy00431k

CATALYSIS SCIENCE & TECHNOLOGY   影响因子和分区

2044-4753

2044-4761

["Molecular catalysts with well-designed structures and abundant metal-nitrogen active sites have received a lot of attention for effective electroreduction of carbon dioxide (ERCD) due to the advantages of having clearly defined active sites for mechanism investigations. However, this metal-nitrogen combination with a fixed electronic structure severely restricts the catalytic efficiency and selectivity, resulting in low production efficiency of more valuable compounds. This work presents the synthesis of metal macrocyclic compounds MPc (M = Fe, Co, Ni, and Zn) through in situ anodic oxidation of N-doped Ti3C2Tx (N-MXene) nanosheets with anchored MPc nanoparticles (named MPc/o-N-MXene). The resulting catalysts exhibit high activity and moreover tailorable selectivity for ERCD on CoPc; CoPc/o-N-MXene shows a faradaic efficiency (FE) for methanol as high as 39.0% with a current density of 32.7 mA cm-2 at -1.0 V (vs. RHE). The oxidation process creates a significant contact between the M-N4 active sites and N-MXene, which regulates the selectivity of ERCD. DFT calculations suggest that only the electronic regulation of Co-N4 by N-doped MXene supports the creation of intermediate *HCO in the generation of methanol in ERCD. Our study presents a new route for the synthesis of efficient catalysts and provides a comprehensive perspective on the mechanism of ERCD on MPc.","Molecular catalysts supported by N-MXene with in situ oxidation have been synthesized by a simple method. Among them, CoPc/o-N-MXene exhibits superior activity and selectivity for ERCD to methanol."]

SCI ; EI

英语

第一 ; 通讯

Key Fundamental Research Project funding from the Shenzhen Science and Technology Innovation Committee["JCYJ20200109141014474","JCYJ20220818100406014"] ; National Natural Science Foundation of China[U19A2089]

Chemistry

Chemistry, Physical

WOS:001267902100001

ROYAL SOC CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China
2.Shenzhen Technol Univ, Coll New Mat & New Energies, Shenzhen 518118, Peoples R China
3.Southern Univ Sci & Technol, Dept Mech & Energy Engn, Shenzhen 518055, Peoples R China
4.Shenzhen Putai Technol Co Ltd, Shenzhen 518055, Peoples R China

Hu, Bihua,Cao, Hailin,Lei, Zhiwei,et al. Electronic regulation & improved conductivity of molecular catalysts as electrocatalysts[J]. CATALYSIS SCIENCE & TECHNOLOGY,2024.

Hu, Bihua.,Cao, Hailin.,Lei, Zhiwei.,Cui, Shuyu.,Wang, Peizhi.,...&Xu, Baomin.(2024).Electronic regulation & improved conductivity of molecular catalysts as electrocatalysts.CATALYSIS SCIENCE & TECHNOLOGY.

Hu, Bihua,et al."Electronic regulation & improved conductivity of molecular catalysts as electrocatalysts".CATALYSIS SCIENCE & TECHNOLOGY (2024).