Molecular Orbital Engineering of Mixed-Addenda Polyoxometalates Boosts Light-Driven Hydrogen Evolution Activity

Manzhou Chi; Ying Zeng; Zhong Ling Lang; Huijie Li; Xing Xin; Yuanyuan Dong; Fangyu Fu; Guo Yu Yang; Hongjin Lv

doi:10.1021/acscatal.4c00295

Molecular Orbital Engineering of Mixed-Addenda Polyoxometalates Boosts Light-Driven Hydrogen Evolution Activity

Manzhou Chi, Ying Zeng, Zhong Ling Lang, Huijie Li, Xing Xin, Yuanyuan Dong, Fangyu Fu, Guo Yu Yang^*, Hongjin Lv^*

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

Inspired by the principle of molecular orbital engineering, two structurally well-defined polyoxometalate (POM)-based hydrogen-evolving catalysts, namely, [H₂N(CH₃)₂]_9.24Na₃H₄[Cu_2.06W_1.94O₂(P₂W₁₆O₆₀)₂]·40H₂O (POM-1) and [H₂N(CH₃)₂]_12.6Na₂H₃[Cu_2.4Mo_6.48W_3.12O₂₆(P₂W₁₂O₄₈)₂]·27H₂O (POM-2), have been successfully synthesized and systematically characterized. Both POM compounds exhibited similar twin-Dawson-type polyoxoanion structures in which the monomer was connected through two μ₂-O atoms bonded to the disordered Cu centers, as revealed by single-crystal X-ray diffraction analyses. Electronic structure analyses confirmed that the introduction of mix-addenda Mo atoms could readily adjust the lowest unoccupied molecular orbital (LUMO) energy level of POM-2, leading to a more negative lowest unoccupied molecular orbital (LUMO) position compared with that of POM-1. Various spectroscopic and theoretical studies confirmed that the molecular orbital engineering modulation of POM-2 could provide a higher driving force for thermodynamically favorable and efficient electron transfer from the photosensitizer to POM-2. In a three-component photocatalytic system, POM-2 exhibited the most efficient photocatalytic hydrogen evolution activity compared to all reported similar catalytic systems, achieving a catalytic turnover number (TON) of 5362 after 6 h of photocatalysis under visible-light irradiation.

Original language	English
Pages (from-to)	5006-5015
Number of pages	10
Journal	ACS Catalysis
Volume	14
Issue number	7
DOIs	https://doi.org/10.1021/acscatal.4c00295
Publication status	Published - 5 Apr 2024

Keywords

hydrogen evolution
mixed-addenda
molecular orbital engineering
photocatalysis
polyoxometalate

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10.1021/acscatal.4c00295

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@article{440d745dae6a46099c9cb82c6b7ba58f,

title = "Molecular Orbital Engineering of Mixed-Addenda Polyoxometalates Boosts Light-Driven Hydrogen Evolution Activity",

abstract = "Inspired by the principle of molecular orbital engineering, two structurally well-defined polyoxometalate (POM)-based hydrogen-evolving catalysts, namely, [H2N(CH3)2]9.24Na3H4[Cu2.06W1.94O2(P2W16O60)2]·40H2O (POM-1) and [H2N(CH3)2]12.6Na2H3[Cu2.4Mo6.48W3.12O26(P2W12O48)2]·27H2O (POM-2), have been successfully synthesized and systematically characterized. Both POM compounds exhibited similar twin-Dawson-type polyoxoanion structures in which the monomer was connected through two μ2-O atoms bonded to the disordered Cu centers, as revealed by single-crystal X-ray diffraction analyses. Electronic structure analyses confirmed that the introduction of mix-addenda Mo atoms could readily adjust the lowest unoccupied molecular orbital (LUMO) energy level of POM-2, leading to a more negative lowest unoccupied molecular orbital (LUMO) position compared with that of POM-1. Various spectroscopic and theoretical studies confirmed that the molecular orbital engineering modulation of POM-2 could provide a higher driving force for thermodynamically favorable and efficient electron transfer from the photosensitizer to POM-2. In a three-component photocatalytic system, POM-2 exhibited the most efficient photocatalytic hydrogen evolution activity compared to all reported similar catalytic systems, achieving a catalytic turnover number (TON) of 5362 after 6 h of photocatalysis under visible-light irradiation.",

keywords = "hydrogen evolution, mixed-addenda, molecular orbital engineering, photocatalysis, polyoxometalate",

author = "Manzhou Chi and Ying Zeng and Lang, {Zhong Ling} and Huijie Li and Xing Xin and Yuanyuan Dong and Fangyu Fu and Yang, {Guo Yu} and Hongjin Lv",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society",

year = "2024",

month = apr,

day = "5",

doi = "10.1021/acscatal.4c00295",

language = "English",

volume = "14",

pages = "5006--5015",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Molecular Orbital Engineering of Mixed-Addenda Polyoxometalates Boosts Light-Driven Hydrogen Evolution Activity

AU - Chi, Manzhou

AU - Zeng, Ying

AU - Lang, Zhong Ling

AU - Li, Huijie

AU - Xin, Xing

AU - Dong, Yuanyuan

AU - Fu, Fangyu

AU - Yang, Guo Yu

AU - Lv, Hongjin

PY - 2024/4/5

Y1 - 2024/4/5

N2 - Inspired by the principle of molecular orbital engineering, two structurally well-defined polyoxometalate (POM)-based hydrogen-evolving catalysts, namely, [H2N(CH3)2]9.24Na3H4[Cu2.06W1.94O2(P2W16O60)2]·40H2O (POM-1) and [H2N(CH3)2]12.6Na2H3[Cu2.4Mo6.48W3.12O26(P2W12O48)2]·27H2O (POM-2), have been successfully synthesized and systematically characterized. Both POM compounds exhibited similar twin-Dawson-type polyoxoanion structures in which the monomer was connected through two μ2-O atoms bonded to the disordered Cu centers, as revealed by single-crystal X-ray diffraction analyses. Electronic structure analyses confirmed that the introduction of mix-addenda Mo atoms could readily adjust the lowest unoccupied molecular orbital (LUMO) energy level of POM-2, leading to a more negative lowest unoccupied molecular orbital (LUMO) position compared with that of POM-1. Various spectroscopic and theoretical studies confirmed that the molecular orbital engineering modulation of POM-2 could provide a higher driving force for thermodynamically favorable and efficient electron transfer from the photosensitizer to POM-2. In a three-component photocatalytic system, POM-2 exhibited the most efficient photocatalytic hydrogen evolution activity compared to all reported similar catalytic systems, achieving a catalytic turnover number (TON) of 5362 after 6 h of photocatalysis under visible-light irradiation.

AB - Inspired by the principle of molecular orbital engineering, two structurally well-defined polyoxometalate (POM)-based hydrogen-evolving catalysts, namely, [H2N(CH3)2]9.24Na3H4[Cu2.06W1.94O2(P2W16O60)2]·40H2O (POM-1) and [H2N(CH3)2]12.6Na2H3[Cu2.4Mo6.48W3.12O26(P2W12O48)2]·27H2O (POM-2), have been successfully synthesized and systematically characterized. Both POM compounds exhibited similar twin-Dawson-type polyoxoanion structures in which the monomer was connected through two μ2-O atoms bonded to the disordered Cu centers, as revealed by single-crystal X-ray diffraction analyses. Electronic structure analyses confirmed that the introduction of mix-addenda Mo atoms could readily adjust the lowest unoccupied molecular orbital (LUMO) energy level of POM-2, leading to a more negative lowest unoccupied molecular orbital (LUMO) position compared with that of POM-1. Various spectroscopic and theoretical studies confirmed that the molecular orbital engineering modulation of POM-2 could provide a higher driving force for thermodynamically favorable and efficient electron transfer from the photosensitizer to POM-2. In a three-component photocatalytic system, POM-2 exhibited the most efficient photocatalytic hydrogen evolution activity compared to all reported similar catalytic systems, achieving a catalytic turnover number (TON) of 5362 after 6 h of photocatalysis under visible-light irradiation.

KW - hydrogen evolution

KW - mixed-addenda

KW - molecular orbital engineering

KW - photocatalysis

KW - polyoxometalate

UR - http://www.scopus.com/inward/record.url?scp=85188253486&partnerID=8YFLogxK

U2 - 10.1021/acscatal.4c00295

DO - 10.1021/acscatal.4c00295

M3 - Article

AN - SCOPUS:85188253486

SN - 2155-5435

VL - 14

SP - 5006

EP - 5015

JO - ACS Catalysis

JF - ACS Catalysis

IS - 7

ER -

Molecular Orbital Engineering of Mixed-Addenda Polyoxometalates Boosts Light-Driven Hydrogen Evolution Activity

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