Catalytic transfer hydroge nation(CTH)of furfural(FF)to furfu ryl alcohol(FFA)has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA...Catalytic transfer hydroge nation(CTH)of furfural(FF)to furfu ryl alcohol(FFA)has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6%FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.展开更多
Our recent theoretical studies have screened out CuCs-doped Ag-based promising catalysts for ethylene epoxidation[ACS Catal.11,3371(2021)].The theoretical results were based on surface modeling,while in the actual rea...Our recent theoretical studies have screened out CuCs-doped Ag-based promising catalysts for ethylene epoxidation[ACS Catal.11,3371(2021)].The theoretical results were based on surface modeling,while in the actual reaction process Ag catalysts are particle shaped.In this work,we combine density functional theory(DFT),Wulff construction theory,and micro kinetic analysis to study the catalytic performance of Ag catalysts at the particle model.It demonstrates that the CuCs-doped Ag catalysts are superior to pure Ag catalysts in terms of selectivity and activity,which is further proved by experimental validation.The characterization analysis finds that both Cu and Cs dopant promote particle growth as well as particle dispersion,resulting in a grain boundary-rich Ag particle.Besides,CuCs also facilitate electrophilic atomic oxygen formation on catalyst surface,which is benefitial for ethylene oxide formation and desorption.Our work provides a case study for catalyst design by combining theory and experiment.展开更多
The fractured surrounding rocks of roadways pose major challenges to safe mining.Grouting has often been used to reinforce the surrounding rocks to mitigate the safety risks associated with fractured rocks.The aim of ...The fractured surrounding rocks of roadways pose major challenges to safe mining.Grouting has often been used to reinforce the surrounding rocks to mitigate the safety risks associated with fractured rocks.The aim of this study is to develop highly efficient composite ultrafine cement(CUC)grouts to reinforce the roadway in fractured surrounding rocks.The materials used are ultrafine cement(UC),ultrafine fly ash(UF),ultrafine slag(US),and additives(superplasticizer[SUP],aluminate ultrafine expansion agent[AUA],gypsum,and retarder).The fluidity,bleeding,shrinkage,setting time,chemical composition,microstructure,degree of hydration,and mechanical property of grouting materials were evaluated in this study.Also,a suitable and effective CUC grout mixture was used to reinforce the roadway in the fractured surrounding rock.The results have shown that the addition of UF and US reduces the plastic viscosity of CUC,and the best fluidity can be obtained by adding 40%UF and 10%US.Since UC and UF particles are small,the pozzolanic effect of UF promotes the hydration reaction,which is conductive to the stability of CUC grouts.In addition,fine particles of UC,UF,and US can effectively fill the pores,while the volumetric expansion of AUA and gypsum decreases the pores and thus affects the microstructure of the solidified grout.The compressive test results have shown that the addition of specific amounts of UF and US can ameliorate the mechanical properties of CUC grouts.Finally,the CUC22‐8 grout was used to reinforce the No.20322 belt roadway.The results of numerical simulation and field monitoring have indicated that grouting can efficaciously reinforce the surrounding rock of the roadway.In this research,high‐performance CUC grouts were developed for surrounding rock reinforcement of underground engineering by utilizing UC and some additives.展开更多
基金supported by the National Natural Science Fund of China(Nos.21776234,21978246)。
文摘Catalytic transfer hydroge nation(CTH)of furfural(FF)to furfu ryl alcohol(FFA)has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6%FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.
基金This work is supported by PetroChina Innovation Foundation(2019D-5007-0403).
文摘Our recent theoretical studies have screened out CuCs-doped Ag-based promising catalysts for ethylene epoxidation[ACS Catal.11,3371(2021)].The theoretical results were based on surface modeling,while in the actual reaction process Ag catalysts are particle shaped.In this work,we combine density functional theory(DFT),Wulff construction theory,and micro kinetic analysis to study the catalytic performance of Ag catalysts at the particle model.It demonstrates that the CuCs-doped Ag catalysts are superior to pure Ag catalysts in terms of selectivity and activity,which is further proved by experimental validation.The characterization analysis finds that both Cu and Cs dopant promote particle growth as well as particle dispersion,resulting in a grain boundary-rich Ag particle.Besides,CuCs also facilitate electrophilic atomic oxygen formation on catalyst surface,which is benefitial for ethylene oxide formation and desorption.Our work provides a case study for catalyst design by combining theory and experiment.
基金supported by the National Natural Science Foundation of China(NSFC)(grant No.52074169,No.51704280)the China Postdoctoral Science Foundation(No.2023M732109)the Opening Foundation of Shandong Key Laboratory of Civil Engineering Disaster Prevention and Mitigation(No.CDPM2021FK02).
文摘The fractured surrounding rocks of roadways pose major challenges to safe mining.Grouting has often been used to reinforce the surrounding rocks to mitigate the safety risks associated with fractured rocks.The aim of this study is to develop highly efficient composite ultrafine cement(CUC)grouts to reinforce the roadway in fractured surrounding rocks.The materials used are ultrafine cement(UC),ultrafine fly ash(UF),ultrafine slag(US),and additives(superplasticizer[SUP],aluminate ultrafine expansion agent[AUA],gypsum,and retarder).The fluidity,bleeding,shrinkage,setting time,chemical composition,microstructure,degree of hydration,and mechanical property of grouting materials were evaluated in this study.Also,a suitable and effective CUC grout mixture was used to reinforce the roadway in the fractured surrounding rock.The results have shown that the addition of UF and US reduces the plastic viscosity of CUC,and the best fluidity can be obtained by adding 40%UF and 10%US.Since UC and UF particles are small,the pozzolanic effect of UF promotes the hydration reaction,which is conductive to the stability of CUC grouts.In addition,fine particles of UC,UF,and US can effectively fill the pores,while the volumetric expansion of AUA and gypsum decreases the pores and thus affects the microstructure of the solidified grout.The compressive test results have shown that the addition of specific amounts of UF and US can ameliorate the mechanical properties of CUC grouts.Finally,the CUC22‐8 grout was used to reinforce the No.20322 belt roadway.The results of numerical simulation and field monitoring have indicated that grouting can efficaciously reinforce the surrounding rock of the roadway.In this research,high‐performance CUC grouts were developed for surrounding rock reinforcement of underground engineering by utilizing UC and some additives.
