Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear s...Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear structure-activity relationship at the atomic level.In this work,we have successfully synthesized atomically precise Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)clusters(PET:2-phenylethanethiol)for HMFOR.Ni^(2+)and S_(2)-with atomic ratio of 1:2 was mainly existed in Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)to form Ni-S bond.The electrochemical test results have suggested both Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)displayed outstanding electrocatalytic ability for HMFOR.The Ni_(6)(PET)_(12)exhibited better electrocatalytic ability than Ni_(4)(PET)_(8)with higher current density,lower overpotential and faster reaction kinetics.The superior electrochemical ability of Ni_(6)(PET)_(12)may be due to the enhanced adsorption towards HMF molecule with strong interaction towards hydroxyl group and furan ring.Moreover,it found that the Ni^(2+)species in Ni_(6)(PET)_(12)could rapidly oxidized into Ni^(3+)species,which could spontaneously capture electron and proton from HMF for oxidation.The theoretical calculation demonstrated that the Ni_(6)(PET)_(12)process lower free energy barrier than Ni_(4)(PET)_(8)to display excellent electrocatalytic performance.This work is of great significance for designing efficient electrocatalysts for HMFOR.展开更多
Electrochemical biomass oxidation has garnered considerable attention due to its low energy consumption and the production of high-value chemicals.Supported metal nanoparticle catalysts have been widely explored in el...Electrochemical biomass oxidation has garnered considerable attention due to its low energy consumption and the production of high-value chemicals.Supported metal nanoparticle catalysts have been widely explored in electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR)but limited by their inhomogeneity to build a clear structure-ability relationship at atomic level.Atomically precise metal nanoclusters with well-defined composition,high purity and unique physichemical property are one kind of ideal model electrocatalyst.In this work,we regulate the microenvironment of catalytic sites in Ni Se_(2)utilizing atomically precise and charge tunnable Au_(25)nanoclusters.The electrochemical results reveal that after the modification of Au_(25)nanoclusters,the HMFOR ability of NiSe_(2)could be enhanced.Among them,the NiSe_(2)modified with Au_(25)^(-)clusters displayed the best electrocatalytic ability,in which the electrons were preferred to transfer from Au_(25)^(-)to NiSe_(2)substrate resulting in the electrons accumulation at the electrocatalyst surface.The enhanced electrochemical performance of electrocatalyst can be attributed to two key factors:(1)enhanced adsorption ability towards HMF due to the strong interaction between electron enriched surface and electrophilic furan rings;(2)fast electron transfer at Au_(25)^(-)/NiSe_(2)interface,resulting in the rapid structure evolution to form active Ni OOH sites.This study serves as a valuable reference for designing highly efficient,atomically precise metal nanocluster electrocatalysts for biomass upgrading.展开更多
基金supported by National Natural Science Foundation of China(No.22102155)the China Postdoctoral Science Foundation(Nos.2021M692909 and 2022T150587).
文摘Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear structure-activity relationship at the atomic level.In this work,we have successfully synthesized atomically precise Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)clusters(PET:2-phenylethanethiol)for HMFOR.Ni^(2+)and S_(2)-with atomic ratio of 1:2 was mainly existed in Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)to form Ni-S bond.The electrochemical test results have suggested both Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)displayed outstanding electrocatalytic ability for HMFOR.The Ni_(6)(PET)_(12)exhibited better electrocatalytic ability than Ni_(4)(PET)_(8)with higher current density,lower overpotential and faster reaction kinetics.The superior electrochemical ability of Ni_(6)(PET)_(12)may be due to the enhanced adsorption towards HMF molecule with strong interaction towards hydroxyl group and furan ring.Moreover,it found that the Ni^(2+)species in Ni_(6)(PET)_(12)could rapidly oxidized into Ni^(3+)species,which could spontaneously capture electron and proton from HMF for oxidation.The theoretical calculation demonstrated that the Ni_(6)(PET)_(12)process lower free energy barrier than Ni_(4)(PET)_(8)to display excellent electrocatalytic performance.This work is of great significance for designing efficient electrocatalysts for HMFOR.
基金supported by the National Natural Science Foundation of China(92061201,21825106 and 22102155)the China Postdoctoral Science Foundation(2021M692909 and 2022T150587)+1 种基金the Thousand Talents(Zhongyuan Scholars)Program of Henan Province(234000510007)the Guangdong Basic and Applied Basic Research Foundation(2023A1515140180)。
文摘Electrochemical biomass oxidation has garnered considerable attention due to its low energy consumption and the production of high-value chemicals.Supported metal nanoparticle catalysts have been widely explored in electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR)but limited by their inhomogeneity to build a clear structure-ability relationship at atomic level.Atomically precise metal nanoclusters with well-defined composition,high purity and unique physichemical property are one kind of ideal model electrocatalyst.In this work,we regulate the microenvironment of catalytic sites in Ni Se_(2)utilizing atomically precise and charge tunnable Au_(25)nanoclusters.The electrochemical results reveal that after the modification of Au_(25)nanoclusters,the HMFOR ability of NiSe_(2)could be enhanced.Among them,the NiSe_(2)modified with Au_(25)^(-)clusters displayed the best electrocatalytic ability,in which the electrons were preferred to transfer from Au_(25)^(-)to NiSe_(2)substrate resulting in the electrons accumulation at the electrocatalyst surface.The enhanced electrochemical performance of electrocatalyst can be attributed to two key factors:(1)enhanced adsorption ability towards HMF due to the strong interaction between electron enriched surface and electrophilic furan rings;(2)fast electron transfer at Au_(25)^(-)/NiSe_(2)interface,resulting in the rapid structure evolution to form active Ni OOH sites.This study serves as a valuable reference for designing highly efficient,atomically precise metal nanocluster electrocatalysts for biomass upgrading.
