Herein,we report a highly active K-added Ru/MgO catalyst for hydrogen storage into aromatic benzyltoluenes at low temperatures to advance liquid organic hydrogen carrier technology.The hydrogenation activity of Ru/K/M...Herein,we report a highly active K-added Ru/MgO catalyst for hydrogen storage into aromatic benzyltoluenes at low temperatures to advance liquid organic hydrogen carrier technology.The hydrogenation activity of Ru/K/MgO catalysts exhibits a volcano-shaped dependence on the K content at the maximum with 0.02 wt%.This is in good agreement with the strength and capacity of H_(2) adsorption derived from basicity,despite a gradual decrease in the textural property and the corresponding increase in the Ru particle size with increasing the K content.Density functional theory calculations show that heterolytic hydrogen adsorption properties(strength and polarization)are facilitated up to a specific density of K on the Ru–MgO interface and excessive K suppresses heterolytic H_(2) adsorption by direct interaction between K and hydrogen,assuring the hydrogenation activity and H_(2) adsorption capability of Ru/K/MgO catalysts.Hence,the Ru/K/MgO catalyst,when K is added in an optimal amount,is highly effective to accelerate hydrogen storage kinetics at low temperatures owing to the enhanced heterolytic H_(2) adsorption.展开更多
CO_(2)utilization powered by sustainable energy offers a promising route to mitigate carbon emissions while producing value-added chemicals[1].Among these pathways,CO_(2)hydrogenation is especially attractive because ...CO_(2)utilization powered by sustainable energy offers a promising route to mitigate carbon emissions while producing value-added chemicals[1].Among these pathways,CO_(2)hydrogenation is especially attractive because it integrates renewable H 2 with carbon resources,which have achieved notable success in producing methanol,CO,etc.[2,3].展开更多
Sulfoxides,a class of pharmaceuticals and fine chemicals of significant importance,are readily peroxidized to sulfones in the H_(2)O_(2) system.Altering the intermediate oxygen species is the key to achieving selectiv...Sulfoxides,a class of pharmaceuticals and fine chemicals of significant importance,are readily peroxidized to sulfones in the H_(2)O_(2) system.Altering the intermediate oxygen species is the key to achieving selectivity regulation.Herein,Zr(OH)4 was used to support Mo species,after calcining at 500℃,obtaining a unique amorphous composite oxide with Mo uniformly dispersed in the ZrO_(2) matrix(Mo_(a)Zr_(0.8)O_(x)-500).Mo_(a)Zr_(0.8)O_(x)-500 demonstrates enhanced catalytic proficiency,enabling the synthesis of sulfoxides within 30 minutes at 30℃.Reactive oxygen species(ROS)quenching experiments and EPR spectra indicate that Mo_(a)Zr_(0.8)O_(x)-500 possesses the ability to rapidly and directly participate in the heterolytic cleavage of H_(2)O_(2) to produce ^(1)O_(2) without passing through the intermediate˙O^(2−),preventing the peroxidation of sulfoxides to sulfones.Additionally,the prevalence of basic sites in Mo_(a)Zr_(0.8)O_(x)-500 is conducive to proton transfer,which plays a significant role in the heterolytic cleavage of H_(2)O_(2).Furthermore,Mo_(a)Zr_(0.8)O_(x)-500 exhibits excellent reproducibility,scalability,and broad substrate applicability.This study provides new insights into the selective regulation of the sulfide oxidation reaction,as well as the preparation of amorphous solid solution.展开更多
Surface regulating the electronic structure and d-band center of electrocatalysts is very much crucial to improving their alkaline hydrogen evolution reaction(HER)performance.Herein,we combined density functional theo...Surface regulating the electronic structure and d-band center of electrocatalysts is very much crucial to improving their alkaline hydrogen evolution reaction(HER)performance.Herein,we combined density functional theory(DFT)computations and experimental studies to prepare and study single transition metal-doped Ni_(3)N nanosheets combined on Ni foam(M-Ni_(3)N,M=V,Cr,Mn,W,Mo,Co and Fe)for ultra-efficient alkaline hydrogen evolution.Physicochemical characterization of as-synthesized M-Ni_(3)N demonstrated that the electrons transferred and aggregated on the catalyst surface,which resulted in their unique electronic structure and chemical composition.DFT computations demonstrated that downshifting of the d-band center weakened the adsorption energy of hydrogen and transition metal doping directly facilitated the adsorption of H_(2)O on M sites(desorption of H on Ni sites)at the surface of M-Ni_(3)N.As a result,a heterolytic cleavage process of water on M-Ni_(3)N nanosheets was formulated,thus drastically boosting the alkaline HER.Specifically,as the best example,the fabricated V-doped Ni_(3)N catalyst exhibited remarkable alkaline HER performance with significantly low overpotential of only 15 mV at a current density of 10 mA cm−2.The strategy exemplified in this work provides a useful way to rational design for highly efficient hydrogen evolution reaction electrocatalysts.展开更多
In the field of catalytic hydro-genation,two primary mecha-nistic pathways,namely the Ho-riuti-Polanyi(HP)mechanism and the non-HP mechanism,have been extensively investi-gated.Current understandings suggested that th...In the field of catalytic hydro-genation,two primary mecha-nistic pathways,namely the Ho-riuti-Polanyi(HP)mechanism and the non-HP mechanism,have been extensively investi-gated.Current understandings suggested that the non-HP mechanism preferred to occur on the coinage metal surfaces,such as copper,silver,and gold,which exhibited low activity towards H_(2) dissociation.Herein,we offered a detailed theoretical investigation into the mechanisms of CO_(2)hydrogenation to formic acid on M_(1)-In_(2)O_(3)(111)surfaces,using density functional theory calculations.Our calculations provided novel in-sights into the preference of the non-HP mechanism on reduced single-atom noble metal cata-lysts,such as r-Rh_(1)-In_(2)O_(3)(111)and r-Ir_(1)-In_(2)O_(3)(111).In these cases,molecularly adsorbed H_(2) would be polarized into H^(δ−)-H^(δ+),thus facilitating the electrophilic attack to the O in CO_(2).Conversely,the H^(δ+)species,derived from heterolytically dissociated H_(2),exhibited a strong affinity on the adjacent oxygen site at the M-O-In interface.This strong adsorption resulted in a higher energy barrier for CO_(2)hydrogenation,thereby rendering the HP mechanism less viable than the non-HP one.Our results were anticipated to provide a deeper understanding of hydrogenation reactions on oxide-supported noble single-atom catalysts and theoretical guidance for the development of novel high-performance catalysts for catalytic hydrogena-tion reactions.展开更多
Atomically dispersed catalysts have demonstrated superior catalytic performance in many chemical transformations.However,limited success has been achieved in applying oxide-supported atomically dis-persed catalysts to...Atomically dispersed catalysts have demonstrated superior catalytic performance in many chemical transformations.However,limited success has been achieved in applying oxide-supported atomically dis-persed catalysts to semihydrogenation of alkynes under mild conditions.展开更多
Metal oxide supported metal catalysts show promising catalytic performance in many industry-relevant reactions.However,the enhancement of performance is often limited by the insufficient metal/metal oxide interface.In...Metal oxide supported metal catalysts show promising catalytic performance in many industry-relevant reactions.However,the enhancement of performance is often limited by the insufficient metal/metal oxide interface.In this work,we demonstrate a general synthesis of Pt-early transition metal oxide(Pt-MO_(x),M=Ti,Zr,V,and Y)catalysts with rich interfacial sites,which is based on the air-induced surface segregation and oxidation of M in the supported Pt-M alloy catalysts.Systematic characterizations verify the dynamic structural response of Pt-M alloy catalysts to air and the formation of Pt-MO_(x) catalysts with abundant interfacial sites.The prepared Pt-TiO_(x) interfacial catalysts exhibit improved performance in hydrogenation reactions of benzaldehyde,nitrobenzene,styrene,and furfural,as a result of the heterolytic dissociation of H_(2) at Pt-metal oxide interfacial sites.展开更多
基金financially supported by the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT,Republic of Korea(2019M3E6A1064908)the Ministry of Education,Republic of Korea(2016R1A6A1A03013422)。
文摘Herein,we report a highly active K-added Ru/MgO catalyst for hydrogen storage into aromatic benzyltoluenes at low temperatures to advance liquid organic hydrogen carrier technology.The hydrogenation activity of Ru/K/MgO catalysts exhibits a volcano-shaped dependence on the K content at the maximum with 0.02 wt%.This is in good agreement with the strength and capacity of H_(2) adsorption derived from basicity,despite a gradual decrease in the textural property and the corresponding increase in the Ru particle size with increasing the K content.Density functional theory calculations show that heterolytic hydrogen adsorption properties(strength and polarization)are facilitated up to a specific density of K on the Ru–MgO interface and excessive K suppresses heterolytic H_(2) adsorption by direct interaction between K and hydrogen,assuring the hydrogenation activity and H_(2) adsorption capability of Ru/K/MgO catalysts.Hence,the Ru/K/MgO catalyst,when K is added in an optimal amount,is highly effective to accelerate hydrogen storage kinetics at low temperatures owing to the enhanced heterolytic H_(2) adsorption.
文摘CO_(2)utilization powered by sustainable energy offers a promising route to mitigate carbon emissions while producing value-added chemicals[1].Among these pathways,CO_(2)hydrogenation is especially attractive because it integrates renewable H 2 with carbon resources,which have achieved notable success in producing methanol,CO,etc.[2,3].
基金supported by the National Natural Science Foundation of China(22278199 and U21B2091)the Fundamental Research Funds for the Central Universities(lzujbky-2023-ct01 and lzujbky-2023-stlt01)+2 种基金the Science and Technology Planning Project of Chengguan District in Lanzhou(2023JSCX0049)the Postdoctoral Fellowship Program of CPSF(GZC20231012)the China Postdoctoral Science Foundation(2024M751263).
文摘Sulfoxides,a class of pharmaceuticals and fine chemicals of significant importance,are readily peroxidized to sulfones in the H_(2)O_(2) system.Altering the intermediate oxygen species is the key to achieving selectivity regulation.Herein,Zr(OH)4 was used to support Mo species,after calcining at 500℃,obtaining a unique amorphous composite oxide with Mo uniformly dispersed in the ZrO_(2) matrix(Mo_(a)Zr_(0.8)O_(x)-500).Mo_(a)Zr_(0.8)O_(x)-500 demonstrates enhanced catalytic proficiency,enabling the synthesis of sulfoxides within 30 minutes at 30℃.Reactive oxygen species(ROS)quenching experiments and EPR spectra indicate that Mo_(a)Zr_(0.8)O_(x)-500 possesses the ability to rapidly and directly participate in the heterolytic cleavage of H_(2)O_(2) to produce ^(1)O_(2) without passing through the intermediate˙O^(2−),preventing the peroxidation of sulfoxides to sulfones.Additionally,the prevalence of basic sites in Mo_(a)Zr_(0.8)O_(x)-500 is conducive to proton transfer,which plays a significant role in the heterolytic cleavage of H_(2)O_(2).Furthermore,Mo_(a)Zr_(0.8)O_(x)-500 exhibits excellent reproducibility,scalability,and broad substrate applicability.This study provides new insights into the selective regulation of the sulfide oxidation reaction,as well as the preparation of amorphous solid solution.
基金the National Natural Science Foundation of China(52222408)MCC Changtian Scientific Research and Development Basic Research Fund(2022JCYJ04)the Ministry of Education’s Industry School Cooperation Collaborative Education Project and Shandong Shandong Weiqiao Pioneering Group Co.,Ltd(220506429071743)for their financial support.
文摘Surface regulating the electronic structure and d-band center of electrocatalysts is very much crucial to improving their alkaline hydrogen evolution reaction(HER)performance.Herein,we combined density functional theory(DFT)computations and experimental studies to prepare and study single transition metal-doped Ni_(3)N nanosheets combined on Ni foam(M-Ni_(3)N,M=V,Cr,Mn,W,Mo,Co and Fe)for ultra-efficient alkaline hydrogen evolution.Physicochemical characterization of as-synthesized M-Ni_(3)N demonstrated that the electrons transferred and aggregated on the catalyst surface,which resulted in their unique electronic structure and chemical composition.DFT computations demonstrated that downshifting of the d-band center weakened the adsorption energy of hydrogen and transition metal doping directly facilitated the adsorption of H_(2)O on M sites(desorption of H on Ni sites)at the surface of M-Ni_(3)N.As a result,a heterolytic cleavage process of water on M-Ni_(3)N nanosheets was formulated,thus drastically boosting the alkaline HER.Specifically,as the best example,the fabricated V-doped Ni_(3)N catalyst exhibited remarkable alkaline HER performance with significantly low overpotential of only 15 mV at a current density of 10 mA cm−2.The strategy exemplified in this work provides a useful way to rational design for highly efficient hydrogen evolution reaction electrocatalysts.
基金supported by the National Key Research and Development Program of Ministry of Sci-ence and Technology of China(No.2022YFA1504601)the National Natural Science Foundation of China(Nos.92045303,22132004,22121001,22072116,22072117,and 21773192).
文摘In the field of catalytic hydro-genation,two primary mecha-nistic pathways,namely the Ho-riuti-Polanyi(HP)mechanism and the non-HP mechanism,have been extensively investi-gated.Current understandings suggested that the non-HP mechanism preferred to occur on the coinage metal surfaces,such as copper,silver,and gold,which exhibited low activity towards H_(2) dissociation.Herein,we offered a detailed theoretical investigation into the mechanisms of CO_(2)hydrogenation to formic acid on M_(1)-In_(2)O_(3)(111)surfaces,using density functional theory calculations.Our calculations provided novel in-sights into the preference of the non-HP mechanism on reduced single-atom noble metal cata-lysts,such as r-Rh_(1)-In_(2)O_(3)(111)and r-Ir_(1)-In_(2)O_(3)(111).In these cases,molecularly adsorbed H_(2) would be polarized into H^(δ−)-H^(δ+),thus facilitating the electrophilic attack to the O in CO_(2).Conversely,the H^(δ+)species,derived from heterolytically dissociated H_(2),exhibited a strong affinity on the adjacent oxygen site at the M-O-In interface.This strong adsorption resulted in a higher energy barrier for CO_(2)hydrogenation,thereby rendering the HP mechanism less viable than the non-HP one.Our results were anticipated to provide a deeper understanding of hydrogenation reactions on oxide-supported noble single-atom catalysts and theoretical guidance for the development of novel high-performance catalysts for catalytic hydrogena-tion reactions.
基金This work was supported by the National Key Research and Development Program of China(2017YFA0207302 and 2017YFA0207303)the National Natural Science Foundation of China(21890752,21731005,21420102001,21573178,and 91845102)the Fundamental Research Funds for Central Universities(20720180026).
文摘Atomically dispersed catalysts have demonstrated superior catalytic performance in many chemical transformations.However,limited success has been achieved in applying oxide-supported atomically dis-persed catalysts to semihydrogenation of alkynes under mild conditions.
基金support from the National Natural Science Foundation of China(Nos.22221003 and 22071225)the Plan for Anhui Major Provincial Science&Technology Project(Nos.202203a0520013 and 2021d05050006)the fellowship of China Postdoctoral Science Foundation(No.2022M712179).
文摘Metal oxide supported metal catalysts show promising catalytic performance in many industry-relevant reactions.However,the enhancement of performance is often limited by the insufficient metal/metal oxide interface.In this work,we demonstrate a general synthesis of Pt-early transition metal oxide(Pt-MO_(x),M=Ti,Zr,V,and Y)catalysts with rich interfacial sites,which is based on the air-induced surface segregation and oxidation of M in the supported Pt-M alloy catalysts.Systematic characterizations verify the dynamic structural response of Pt-M alloy catalysts to air and the formation of Pt-MO_(x) catalysts with abundant interfacial sites.The prepared Pt-TiO_(x) interfacial catalysts exhibit improved performance in hydrogenation reactions of benzaldehyde,nitrobenzene,styrene,and furfural,as a result of the heterolytic dissociation of H_(2) at Pt-metal oxide interfacial sites.
