Co–In Bimetallic Hydroxide Nanosheet Arrays With Coexisting Hydroxyl and Metal Vacancies Anchored on Rod‐Like MOF Template for Enhanced Photocatalytic CO2 Reduction

Abstract Layered double hydroxides (LDHs) can serves as catalysts for CO2 photocatalytic reduction (CO2PR). However, the conventionally synthesized LDHs undergo undesired aggregation, which results in an insufficient number of active sites and limits the desirable electron transfer required for CO2P...

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Main Authors: Jingjuan Feng, Weiwei Li, Tianxia Chen, Zhaopeng Zeng, Meng Tian, Wenxin Ji, Yan Guo, Shixiong Min, Xiangyu Liu
Format: Article
Language:English
Published: Wiley 2025-01-01
Series:Advanced Science
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Online Access:https://doi.org/10.1002/advs.202411673
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author Jingjuan Feng
Weiwei Li
Tianxia Chen
Zhaopeng Zeng
Meng Tian
Wenxin Ji
Yan Guo
Shixiong Min
Xiangyu Liu
author_facet Jingjuan Feng
Weiwei Li
Tianxia Chen
Zhaopeng Zeng
Meng Tian
Wenxin Ji
Yan Guo
Shixiong Min
Xiangyu Liu
author_sort Jingjuan Feng
collection DOAJ
description Abstract Layered double hydroxides (LDHs) can serves as catalysts for CO2 photocatalytic reduction (CO2PR). However, the conventionally synthesized LDHs undergo undesired aggregation, which results in an insufficient number of active sites and limits the desirable electron transfer required for CO2PR. The metal‐organic framework (MOF) template‐grown LDHs demonstrate excellent promise for exploiting the strengths of both MOFs and LDHs. Herein, the in situ growth of MIL‐68(In)‐NH2 MOF‐templated Co–In bimetallic catalyst (CoIn‐LDH/MOF) having an ultrathin nanosheet morphology on the preserved rod‐like MOF template is demonstrated. Compared to the conventionally grown bimetallic LDH (CoIn‐LDH), CoIn‐LDH/MOF not only exposes more active sites but also possesses hydroxyl vacancies (VOH) and Co vacancies (VCo). Thus, CoIn‐LDH/MOF performs a higher CO generation rate of 2320 µmol g−1 h−1 during CO2PR, demonstrating improved activity and selectivity than those in CoIn‐LDH. Experiments coupled with calculations reveal that the CoIn‐LDH/MOF‐driven CO2PR follows the *COOH pathway. The lower energy barriers for the formation of *COOH and CO(g) can be attributed to the coexistence of VOH and VCo in CoIn‐LDH/MOF, effectively promoting charge transfer and enhancing CO2PR performance. This study provides a new strategy to obtain high‐performant LDH‐based catalysts with improved morphology.
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spelling doaj-art-8affd44df7b641e1a4cefa6fd74218192025-01-29T09:50:19ZengWileyAdvanced Science2198-38442025-01-01124n/an/a10.1002/advs.202411673Co–In Bimetallic Hydroxide Nanosheet Arrays With Coexisting Hydroxyl and Metal Vacancies Anchored on Rod‐Like MOF Template for Enhanced Photocatalytic CO2 ReductionJingjuan Feng0Weiwei Li1Tianxia Chen2Zhaopeng Zeng3Meng Tian4Wenxin Ji5Yan Guo6Shixiong Min7Xiangyu Liu8State Key Laboratory of High‐efficiency Utilization of Coal and Green Chemical Engineering College of Chemistry and Chemical Engineering Ningxia University Yinchuan 750021 ChinaState Key Laboratory of High‐efficiency Utilization of Coal and Green Chemical Engineering College of Chemistry and Chemical Engineering Ningxia University Yinchuan 750021 ChinaState Key Laboratory of High‐efficiency Utilization of Coal and Green Chemical Engineering College of Chemistry and Chemical Engineering Ningxia University Yinchuan 750021 ChinaState Key Laboratory of High‐efficiency Utilization of Coal and Green Chemical Engineering College of Chemistry and Chemical Engineering Ningxia University Yinchuan 750021 ChinaState Key Laboratory of High‐efficiency Utilization of Coal and Green Chemical Engineering College of Chemistry and Chemical Engineering Ningxia University Yinchuan 750021 ChinaState Key Laboratory of High‐efficiency Utilization of Coal and Green Chemical Engineering College of Chemistry and Chemical Engineering Ningxia University Yinchuan 750021 ChinaState Key Laboratory of High‐efficiency Utilization of Coal and Green Chemical Engineering College of Chemistry and Chemical Engineering Ningxia University Yinchuan 750021 ChinaSchool of Chemistry and Chemical Engineering North Minzu University Yinchuan 750021 ChinaState Key Laboratory of High‐efficiency Utilization of Coal and Green Chemical Engineering College of Chemistry and Chemical Engineering Ningxia University Yinchuan 750021 ChinaAbstract Layered double hydroxides (LDHs) can serves as catalysts for CO2 photocatalytic reduction (CO2PR). However, the conventionally synthesized LDHs undergo undesired aggregation, which results in an insufficient number of active sites and limits the desirable electron transfer required for CO2PR. The metal‐organic framework (MOF) template‐grown LDHs demonstrate excellent promise for exploiting the strengths of both MOFs and LDHs. Herein, the in situ growth of MIL‐68(In)‐NH2 MOF‐templated Co–In bimetallic catalyst (CoIn‐LDH/MOF) having an ultrathin nanosheet morphology on the preserved rod‐like MOF template is demonstrated. Compared to the conventionally grown bimetallic LDH (CoIn‐LDH), CoIn‐LDH/MOF not only exposes more active sites but also possesses hydroxyl vacancies (VOH) and Co vacancies (VCo). Thus, CoIn‐LDH/MOF performs a higher CO generation rate of 2320 µmol g−1 h−1 during CO2PR, demonstrating improved activity and selectivity than those in CoIn‐LDH. Experiments coupled with calculations reveal that the CoIn‐LDH/MOF‐driven CO2PR follows the *COOH pathway. The lower energy barriers for the formation of *COOH and CO(g) can be attributed to the coexistence of VOH and VCo in CoIn‐LDH/MOF, effectively promoting charge transfer and enhancing CO2PR performance. This study provides a new strategy to obtain high‐performant LDH‐based catalysts with improved morphology.https://doi.org/10.1002/advs.202411673catalytic reductionCO2 photoreductionlayered double hydroxidesmetal‐organic frameworkultrathin nanosheets
spellingShingle Jingjuan Feng
Weiwei Li
Tianxia Chen
Zhaopeng Zeng
Meng Tian
Wenxin Ji
Yan Guo
Shixiong Min
Xiangyu Liu
Co–In Bimetallic Hydroxide Nanosheet Arrays With Coexisting Hydroxyl and Metal Vacancies Anchored on Rod‐Like MOF Template for Enhanced Photocatalytic CO2 Reduction
Advanced Science
catalytic reduction
CO2 photoreduction
layered double hydroxides
metal‐organic framework
ultrathin nanosheets
title Co–In Bimetallic Hydroxide Nanosheet Arrays With Coexisting Hydroxyl and Metal Vacancies Anchored on Rod‐Like MOF Template for Enhanced Photocatalytic CO2 Reduction
title_full Co–In Bimetallic Hydroxide Nanosheet Arrays With Coexisting Hydroxyl and Metal Vacancies Anchored on Rod‐Like MOF Template for Enhanced Photocatalytic CO2 Reduction
title_fullStr Co–In Bimetallic Hydroxide Nanosheet Arrays With Coexisting Hydroxyl and Metal Vacancies Anchored on Rod‐Like MOF Template for Enhanced Photocatalytic CO2 Reduction
title_full_unstemmed Co–In Bimetallic Hydroxide Nanosheet Arrays With Coexisting Hydroxyl and Metal Vacancies Anchored on Rod‐Like MOF Template for Enhanced Photocatalytic CO2 Reduction
title_short Co–In Bimetallic Hydroxide Nanosheet Arrays With Coexisting Hydroxyl and Metal Vacancies Anchored on Rod‐Like MOF Template for Enhanced Photocatalytic CO2 Reduction
title_sort co in bimetallic hydroxide nanosheet arrays with coexisting hydroxyl and metal vacancies anchored on rod like mof template for enhanced photocatalytic co2 reduction
topic catalytic reduction
CO2 photoreduction
layered double hydroxides
metal‐organic framework
ultrathin nanosheets
url https://doi.org/10.1002/advs.202411673
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