Molecular Design of Dispersed Nickel Phthalocyanine@Nanocarbon Hybrid Catalyst for Active and Stable Electroreduction of CO2

Zhang, Zisheng1,2; Wang, Yang-Gang1

2021-07-01

10.1021/acs.jpcc.1c02508

Journal of Physical Chemistry C   影响因子和分区

1932-7447

1932-7455

The molecular catalyst/nanocarbon hybrid through pi-pi stacking immobilization is an emerging family of single-atom catalysts with outstanding performance in electrocatalysis, well-defined active site, and tunability at molecular level through functional group substitution. In the present work, we provide a general strategy for the rational design of molecular single-atom catalyst in the form of nickel phthalocyanine@nanocarbon (NiPc@NC) for highly efficient electroreduction of CO2 to CO. We employ density functional theory (DFT) calculations and state-of-the-art electronic structure analysis to explore the mechanism and substituent effects on structural stability, redox chemistry, adsorption properties, and molecule- substrate interactions of the NiPc catalyst. We have revealed that the electron-withdrawing groups facilitate the reductive activation of the catalytic Ni center but weaken the Ni-N bond strength and make the CO desorption sluggish, while the electron-donating groups do the opposite. A substituent-dependent correlation between interaction strength and electron transfer through the interface is also revealed by noncovalent interaction analysis and electron density difference projection. On the basis of the gained insights, we apply semiempirical quantum mechanical (SQM) calculation, machine learning (ML), and genetic algorithm (GA) to screening through the chemical space of ca. 10 trillion substituted NiPc molecules under a descriptor scheme to identify promising molecular candidates for the NiPc@NC hybrid material. The best candidate from GA search outperforms the state-of-the-art catalyst in terms of stability, reduction potential (improved by 110 mV), and interaction with substrate (strengthened by 0.46 eV). Design strategies are proposed based on the top-scoring molecules from computational screening, and the workflow is highly generalizable and transferable to similar molecular systems for other applications.

SCI ; EI

英语

第一 ; 通讯

NSFC of China[22022504] ; Guangdong "Pearl River" Talent Plan[2019QN01L353] ; Higher Education Innovation Strong School Project of Guangdong Province of China[2020KTSCX122] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry ; Science & Technology - Other Topics ; Materials Science

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:000670787500013

AMER CHEMICAL SOC

20212910662027

Carbon dioxide ; Catalyst activity ; Chemical analysis ; Computation theory ; Density functional theory ; Design for testability ; Electrocatalysis ; Electrolytic reduction ; Electron transport properties ; Electronic structure ; Genetic algorithms ; Hybrid materials ; Ions ; Machine learning ; Molecules ; Nickel ; Quantum theory ; Stability ; Substrates

Ore Treatment:533.1 ; Nickel:548.1 ; Computer Theory, Includes Formal Logic, Automata Theory, Switching Theory, Programming Theory:721.1 ; Electrochemistry:801.4.1 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Univ Calif Los Angeles, Dept Chem & Biochem, 607 Charles E Young Dr East, Los Angeles, CA 90095 USA

Zhang, Zisheng,Wang, Yang-Gang. Molecular Design of Dispersed Nickel Phthalocyanine@Nanocarbon Hybrid Catalyst for Active and Stable Electroreduction of CO2[J]. Journal of Physical Chemistry C,2021,125(25):13836-13849.

Zhang, Zisheng,&Wang, Yang-Gang.(2021).Molecular Design of Dispersed Nickel Phthalocyanine@Nanocarbon Hybrid Catalyst for Active and Stable Electroreduction of CO2.Journal of Physical Chemistry C,125(25),13836-13849.

Zhang, Zisheng,et al."Molecular Design of Dispersed Nickel Phthalocyanine@Nanocarbon Hybrid Catalyst for Active and Stable Electroreduction of CO2".Journal of Physical Chemistry C 125.25(2021):13836-13849.