Photocatalytic hydrogen evolution reaction(HER)represents one of the most promising technologies for sus-tainable development.Even though metal-organic framework(MOF),comprising rich topologies and tunable functionali...Photocatalytic hydrogen evolution reaction(HER)represents one of the most promising technologies for sus-tainable development.Even though metal-organic framework(MOF),comprising rich topologies and tunable functionalities,is getting attention as a new generation of photocatalyst,a majority of them only provide unclear active sites along with the use of external noble-metal based photosensitizers and environmentally unfriendly scavengers.Therefore,it is urged to develop MOFs possessing structurally unambiguous active sites along with inherent photosensitizing units and execute photocatalytic HER with greener sacrificial reagents.Herein,we report a UiO-66-type framework,namely UiO-66-dcbdt-Cd(dcbdt^(2-)=1,4-dicarboxylatebenzene-2,3-dithiol),bearing Cd-thiocatecholato moieties as intrinsic photosensitizing units and structurally well-defined active sites for photocatalytic HER in H_(2)O.UiO-66-dcbdt-Cd gave the best HER yield of 5.29 mmol g^(-1)and rate of 1.32 mmol g^(-1)h^(-1),outperforming the negligible HER performance of pristine metal-free UiO-66-dcbdt.This work provides insight to manipulation of thhiocatecholate functionalities inside MOFs to construct inherent photosensitizing units as well as stable structurally unambiguous active sites for sustainable photocatalytic applications.展开更多
基金funded by the Foundation of Basic and Applied Basic Research of Guangdong Province(2020B1515120024)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01Z032)Science and Technology Program of Guangzhou(202201010244).
文摘Photocatalytic hydrogen evolution reaction(HER)represents one of the most promising technologies for sus-tainable development.Even though metal-organic framework(MOF),comprising rich topologies and tunable functionalities,is getting attention as a new generation of photocatalyst,a majority of them only provide unclear active sites along with the use of external noble-metal based photosensitizers and environmentally unfriendly scavengers.Therefore,it is urged to develop MOFs possessing structurally unambiguous active sites along with inherent photosensitizing units and execute photocatalytic HER with greener sacrificial reagents.Herein,we report a UiO-66-type framework,namely UiO-66-dcbdt-Cd(dcbdt^(2-)=1,4-dicarboxylatebenzene-2,3-dithiol),bearing Cd-thiocatecholato moieties as intrinsic photosensitizing units and structurally well-defined active sites for photocatalytic HER in H_(2)O.UiO-66-dcbdt-Cd gave the best HER yield of 5.29 mmol g^(-1)and rate of 1.32 mmol g^(-1)h^(-1),outperforming the negligible HER performance of pristine metal-free UiO-66-dcbdt.This work provides insight to manipulation of thhiocatecholate functionalities inside MOFs to construct inherent photosensitizing units as well as stable structurally unambiguous active sites for sustainable photocatalytic applications.
