Comprehensive analysis of the connection be-tween surface metal species and the mechanism of hydrogen(H_(2))generation on TiO_(2)provides important new information for the develop-ment of more effective catalysts for ...Comprehensive analysis of the connection be-tween surface metal species and the mechanism of hydrogen(H_(2))generation on TiO_(2)provides important new information for the develop-ment of more effective catalysts for H_(2) produc-tion.We have systematically investigated the mechanism of catalytic H_(2) generation on the Cu_(10)/TiO_(2),Au_(10)/TiO_(2),Au_(8)Cu_(2)/TiO_(2)and Cu_(1)/Au_(8)Cu_(2)/TiO_(2)surfaces using density func-tional theory.Our results demonstrate an O-H^(δ+)···H^(δ−)-M type transition state for H_(2) production,and the Au_(8)Cu_(2)(0.54 eV)bimetal-lic cluster catalyst exhibits more activity in comparison to the Cu_(10)(0.63 eV)and Au_(10)(0.88 eV)cluster catalysts on the TiO_(2)surface.On the Cu_(1)/Au_(8)Cu_(2)/TiO_(2)surface,we found that Au_(8)Cu_(2)clusters act as electron donors,while Cu single atom acts as an electron acceptor.Therefore,the Au_(8)Cu_(2)bimetallic catalyst has a low energy barrier(0.58 eV)in the reductive reaction of H_(2) production in water,but Cu single atom as the catalytic center has a higher en-ergy barrier(1.49 eV).This implies that bimetallic catalysts may be able to catalyze the wa-ter dehydrogenation reaction more successfully,which would be important knowledge for comprehending and refining the photocatalytic H_(2) generation process.展开更多
A highly enantioselective Piers-type hydrosilylation of simple ketones was successfully realized using a chiral frustrated Lewis pair of tri-tert-butylphosphine and chiral diene-derived borane as catalyst.A wide range...A highly enantioselective Piers-type hydrosilylation of simple ketones was successfully realized using a chiral frustrated Lewis pair of tri-tert-butylphosphine and chiral diene-derived borane as catalyst.A wide range of optically active secondary alcohols were furnished in 80%-99% yields with 81%-97% ee's under mild reaction conditions.展开更多
基金supported by the National Natural Science Foundation of China(No.22473107)。
文摘Comprehensive analysis of the connection be-tween surface metal species and the mechanism of hydrogen(H_(2))generation on TiO_(2)provides important new information for the develop-ment of more effective catalysts for H_(2) produc-tion.We have systematically investigated the mechanism of catalytic H_(2) generation on the Cu_(10)/TiO_(2),Au_(10)/TiO_(2),Au_(8)Cu_(2)/TiO_(2)and Cu_(1)/Au_(8)Cu_(2)/TiO_(2)surfaces using density func-tional theory.Our results demonstrate an O-H^(δ+)···H^(δ−)-M type transition state for H_(2) production,and the Au_(8)Cu_(2)(0.54 eV)bimetal-lic cluster catalyst exhibits more activity in comparison to the Cu_(10)(0.63 eV)and Au_(10)(0.88 eV)cluster catalysts on the TiO_(2)surface.On the Cu_(1)/Au_(8)Cu_(2)/TiO_(2)surface,we found that Au_(8)Cu_(2)clusters act as electron donors,while Cu single atom acts as an electron acceptor.Therefore,the Au_(8)Cu_(2)bimetallic catalyst has a low energy barrier(0.58 eV)in the reductive reaction of H_(2) production in water,but Cu single atom as the catalytic center has a higher en-ergy barrier(1.49 eV).This implies that bimetallic catalysts may be able to catalyze the wa-ter dehydrogenation reaction more successfully,which would be important knowledge for comprehending and refining the photocatalytic H_(2) generation process.
基金We are grateful for generous financial support from the National Natural Science Foundation of China (.21572231,21521002,and 21825108).
文摘A highly enantioselective Piers-type hydrosilylation of simple ketones was successfully realized using a chiral frustrated Lewis pair of tri-tert-butylphosphine and chiral diene-derived borane as catalyst.A wide range of optically active secondary alcohols were furnished in 80%-99% yields with 81%-97% ee's under mild reaction conditions.
