Here we propose a new concept of"molecule aging":with some special treatment,a molecule could be"aged"by losing some unknown tiny particles or pieces from atoms in the molecule,Such"aging"...Here we propose a new concept of"molecule aging":with some special treatment,a molecule could be"aged"by losing some unknown tiny particles or pieces from atoms in the molecule,Such"aging"or loss of unknown tiny particles does not change apparently its molecular structure or chemical composition,but some physicochemical properties could be changed irreversibly.We further confirm such"molecule aging"via a long-term electron attacking to age water(H_(2)O)molecules.The IR spectra show no structural difference between the fresh water and the aged one,while the NMR spectra show that the electron attacking can decrease the size of water clusters.Such facts indicate that the electron attacking indeed can"affect"the structure of water molecule slightly but without damaging to its basic molecule frame.Further exploration reveals that the hydrogen evolution reaction(HER)activity of the aged water molecule is lower than the fresh water on the same Pt/C electrocatalyst.The density functional theory calculations indicate that the shortened O-H bond in H_(2)O indeed can present lower HER activity,so the observed size decrease of water clusters from NMR probably could be attributed to the shortening of O-H bond in water molecules.Such results indicate significantly that the molecule aging can produce materials with new functions for new possible applications.展开更多
In this study,phosphorus doped graphene supported PtNiP nanocluster electrocatalyst(PtNiP/P-graphene)was successfully prepared via a simple hypophosphite-assisted co-reduction method.The improved anchoring force and i...In this study,phosphorus doped graphene supported PtNiP nanocluster electrocatalyst(PtNiP/P-graphene)was successfully prepared via a simple hypophosphite-assisted co-reduction method.The improved anchoring force and increased anchoring sites of graphene support result from phosphorus doping as well as size-confined growth effect of NaH_(2)PO_(2) leads to uniform dispersion of ultrafine PtNiP nanoclusters.Doped P also promotes the removal of CO-like intermediate by adjusting Pt electronic structure combining with alloyed Ni via electronic effects.As a result,the as-prepared PtNiP/P-graphene catalyst with more exposed active sites and optimized electronic structure of Pt alloy shows excellent electrocatalytic performances for methanol oxidation reaction(MOR)both in activity and durability in an acidic medium.展开更多
基金funded by the Key Research and Development Program sponsored by the Ministry of Science and Technology(MOST)(2022YFA1203400)National Natural Science Foundation of China(21925205,22072145,21372155,22005294,and 22102172)。
文摘Here we propose a new concept of"molecule aging":with some special treatment,a molecule could be"aged"by losing some unknown tiny particles or pieces from atoms in the molecule,Such"aging"or loss of unknown tiny particles does not change apparently its molecular structure or chemical composition,but some physicochemical properties could be changed irreversibly.We further confirm such"molecule aging"via a long-term electron attacking to age water(H_(2)O)molecules.The IR spectra show no structural difference between the fresh water and the aged one,while the NMR spectra show that the electron attacking can decrease the size of water clusters.Such facts indicate that the electron attacking indeed can"affect"the structure of water molecule slightly but without damaging to its basic molecule frame.Further exploration reveals that the hydrogen evolution reaction(HER)activity of the aged water molecule is lower than the fresh water on the same Pt/C electrocatalyst.The density functional theory calculations indicate that the shortened O-H bond in H_(2)O indeed can present lower HER activity,so the observed size decrease of water clusters from NMR probably could be attributed to the shortening of O-H bond in water molecules.Such results indicate significantly that the molecule aging can produce materials with new functions for new possible applications.
基金supported by the National Natural Science Foundation of China(Nos.21733004,U1601211,21673221,21733004,21603216,and U19A2016)the National Science and Technology Major Project(No.2018YFB1502703)+1 种基金Jilin Province Science and Technology Development Program(Nos.20170520150IH,20180101030JC,20190201270JC,and 20200201001JC)the Chinese Academy of Sciences STS Project(No.KFJ-STS-ZDTP-088).
文摘In this study,phosphorus doped graphene supported PtNiP nanocluster electrocatalyst(PtNiP/P-graphene)was successfully prepared via a simple hypophosphite-assisted co-reduction method.The improved anchoring force and increased anchoring sites of graphene support result from phosphorus doping as well as size-confined growth effect of NaH_(2)PO_(2) leads to uniform dispersion of ultrafine PtNiP nanoclusters.Doped P also promotes the removal of CO-like intermediate by adjusting Pt electronic structure combining with alloyed Ni via electronic effects.As a result,the as-prepared PtNiP/P-graphene catalyst with more exposed active sites and optimized electronic structure of Pt alloy shows excellent electrocatalytic performances for methanol oxidation reaction(MOR)both in activity and durability in an acidic medium.
