CONSPECTUS:Supported metal catalyst,has been one of the most important systems in the field of heterogeneous catalysis.The great complexity of both the compositions and structures of such supported metal catalysts pro...CONSPECTUS:Supported metal catalyst,has been one of the most important systems in the field of heterogeneous catalysis.The great complexity of both the compositions and structures of such supported metal catalysts provides a great degree of freedom for tuning their catalytic properties,which has essentially triggered the explosive growth in research on design and control active metals’surface structures for decades.An ideal metal catalyst theoretically features maximum active sites and optimal intrinsic reactivity to facilitate a desired chemical reaction.Inspired by the catalytic concepts brought by natural enzymes and homogeneous catalysis,the fabrication of heterogeneous catalysts with atomically dispersed metal atoms has attracted much attention and been extensively explored in recent years.Atomically dispersed metal catalysts(ADMCs)including single-atom catalyst(SACs)and fully exposed cluster catalyst(FECCs),as shining stars in heterogeneous catalysts have recently drawn much attention.The advantages of ADMCs mainly include the following three aspects:(1)the fully exposed active metal atoms can realize the utmost atomic utilization efficiency and reduce the cost of catalysts;(2)the geometric and electronic structure can be effectively regulated by altering the coordination environments of metal atoms and then further tuning the catalytic performance in terms of activity,selectivity,and stability;(3)the precisely designed structures provide a promising platform for digging the structure−performance relationships of active sites with the assistance of theoretical calculations.Owing to these advantages,ADMCs have been used in thermal-catalysis,electrocatalysis,photocatalysis,etc.until now.In this Account,a summary of recent progress regarding ADMCs for heterogeneous thermal catalysis in our group will be presented from the following aspects.First,an overview of great opportunities brought by nanodiamond and its derivatives as substrates for anchoring atomically dispersed metals(ADMs)and tailoring their structures.Next,our recent progress in achieving desirable catalytic performance,including activity,selectivity,and stability over nanodiamond−graphene(ND@G)supported ADMCs will be introduced in detail.Finally,a brief outlook regarding the development directions for ADMCs by discussing current challenges and opportunities will be proposed.It is hoped that this Account can inspire the development of the rational design and various application of ADMCs.展开更多
Processes for the isomerization of light alkanes have been commercialized;however,the isomerization of paraffins(C_(n)H_(2n+2),n≥7)remains a challenge.On mesoporous tungsten-zirconia catalyst supported Pt catalysts(P...Processes for the isomerization of light alkanes have been commercialized;however,the isomerization of paraffins(C_(n)H_(2n+2),n≥7)remains a challenge.On mesoporous tungsten-zirconia catalyst supported Pt catalysts(Pt/WZrOx),initial isomerization productivity of 5249 moli-C7/molPt/h was obtained for n-heptane reforming at 275°C and 5 bar of hydrogen.展开更多
The pursuit of energy conservation and environmental protection has always been a hot topic in the catalytic fields,which is inseparable from the rational designing of efficient catalysts and an in-depth understanding...The pursuit of energy conservation and environmental protection has always been a hot topic in the catalytic fields,which is inseparable from the rational designing of efficient catalysts and an in-depth understanding of the catalytic reaction mechanism.In this work,fully-exposed Pt clusters were fabricated on the atomically dispersed Sn decorated nanodiamond/graphene(Sn-ND@G)hybrid support and employed for direct dehydrogenation(DDH)of ethylbenzene(EB)to styrene(ST).The detailed structural characterizations revealed the fully-exposed Pt clusters were stabilized on Sn-ND@G,assisted by the spatial separation of atomically dispersed Sn species.The as-prepared Pt/Sn-ND@G catalyst showed enhanced ST yield(136.2 molEB·molpt-1·h-1 EB conversion rate and 99.7%ST selectivity)and robust long-term stability at 500℃for the EB DDH reaction,compared with the traditional ND@G supported Pt nanoparticle catalyst(Pt/ND@G).The ST prefers to desorb from the fully-exposed Pt clusters,resulting in the enhanced DDH catalytic performance of the Pt/Sn-ND@G catalyst.The present work paves a new way for designing highly dispersed and stable supported metal catalysts for DDH reactions.展开更多
基金supported by the National Key R&D Program of China(2022 YFA 1504500,2022YFB4003100,2021YFA1502802)the National Natural Science Foundation of China(22202213,22072162,92145301,U21B2092,21961160722,91845201,22202004)+6 种基金the Chinese Academy of Sciences(172GJHZ2022028MI)the Dalian National Lab for Clean Energy(DNL Cooperation Fund 202001)the Science and Technology Program of Sichuan Province(2021YFSY0021)the China Petroleum&Chemical Corporation(No.420043-2)F.Huang acknowledges the support from China Postdoctoral Science Foundation(2021M703279)the Science and Technology Plan from Liaoning Province(2022-BS-002)the Innovation Foundation from Institute of Metal Research(2022-PY15).
文摘CONSPECTUS:Supported metal catalyst,has been one of the most important systems in the field of heterogeneous catalysis.The great complexity of both the compositions and structures of such supported metal catalysts provides a great degree of freedom for tuning their catalytic properties,which has essentially triggered the explosive growth in research on design and control active metals’surface structures for decades.An ideal metal catalyst theoretically features maximum active sites and optimal intrinsic reactivity to facilitate a desired chemical reaction.Inspired by the catalytic concepts brought by natural enzymes and homogeneous catalysis,the fabrication of heterogeneous catalysts with atomically dispersed metal atoms has attracted much attention and been extensively explored in recent years.Atomically dispersed metal catalysts(ADMCs)including single-atom catalyst(SACs)and fully exposed cluster catalyst(FECCs),as shining stars in heterogeneous catalysts have recently drawn much attention.The advantages of ADMCs mainly include the following three aspects:(1)the fully exposed active metal atoms can realize the utmost atomic utilization efficiency and reduce the cost of catalysts;(2)the geometric and electronic structure can be effectively regulated by altering the coordination environments of metal atoms and then further tuning the catalytic performance in terms of activity,selectivity,and stability;(3)the precisely designed structures provide a promising platform for digging the structure−performance relationships of active sites with the assistance of theoretical calculations.Owing to these advantages,ADMCs have been used in thermal-catalysis,electrocatalysis,photocatalysis,etc.until now.In this Account,a summary of recent progress regarding ADMCs for heterogeneous thermal catalysis in our group will be presented from the following aspects.First,an overview of great opportunities brought by nanodiamond and its derivatives as substrates for anchoring atomically dispersed metals(ADMs)and tailoring their structures.Next,our recent progress in achieving desirable catalytic performance,including activity,selectivity,and stability over nanodiamond−graphene(ND@G)supported ADMCs will be introduced in detail.Finally,a brief outlook regarding the development directions for ADMCs by discussing current challenges and opportunities will be proposed.It is hoped that this Account can inspire the development of the rational design and various application of ADMCs.
基金support from the Natural Science Foundation of China(nos.21725301,21932002,22005007,and 21821004)the National Key R&DProgram of China(no.2017YFB0602200)and the Chinese Postdoctoral Science Foundation(no.8206300246).B.Z.gratefully acknowledges the support of the Boya Postdoctoral Fellowship of Peking University(2019–2020)and the Junior Fellowship of Beijing National Laboratory of Molecular Science(BMS Junior Fellow,2020–2023).D.M.acknowledges support from the Tencent Foundation through the XPLORER PRIZE and the support from OSSO state key lab。
文摘Processes for the isomerization of light alkanes have been commercialized;however,the isomerization of paraffins(C_(n)H_(2n+2),n≥7)remains a challenge.On mesoporous tungsten-zirconia catalyst supported Pt catalysts(Pt/WZrOx),initial isomerization productivity of 5249 moli-C7/molPt/h was obtained for n-heptane reforming at 275°C and 5 bar of hydrogen.
基金supported by the National Key Research and Development Program of China(No.2021YFA1502802)the National Natural Science Foundation of China(Nos.21961160722,92145301,U21B2092,22072162,and 91845201)+5 种基金the Liaoning Revitalization Talents Program(No.XLYC1907055)Natural Science Foundation of Liaoning Province(No.2021-MS001)IMR Innovation Fund(No.2022-PY05)Dalian National Lab for Clean Energy(No.DNL Cooperation Fund 202001)the Sinopec China.N.W.hereby acknowledges the funding support from the Research Grants Council of Hong Kong(Nos.C6021-14E,N_HKUST624/19,and 16306818)The XAS experiments were conducted in Shanghai Synchrotron Radiation Facility(SSRF)。
文摘The pursuit of energy conservation and environmental protection has always been a hot topic in the catalytic fields,which is inseparable from the rational designing of efficient catalysts and an in-depth understanding of the catalytic reaction mechanism.In this work,fully-exposed Pt clusters were fabricated on the atomically dispersed Sn decorated nanodiamond/graphene(Sn-ND@G)hybrid support and employed for direct dehydrogenation(DDH)of ethylbenzene(EB)to styrene(ST).The detailed structural characterizations revealed the fully-exposed Pt clusters were stabilized on Sn-ND@G,assisted by the spatial separation of atomically dispersed Sn species.The as-prepared Pt/Sn-ND@G catalyst showed enhanced ST yield(136.2 molEB·molpt-1·h-1 EB conversion rate and 99.7%ST selectivity)and robust long-term stability at 500℃for the EB DDH reaction,compared with the traditional ND@G supported Pt nanoparticle catalyst(Pt/ND@G).The ST prefers to desorb from the fully-exposed Pt clusters,resulting in the enhanced DDH catalytic performance of the Pt/Sn-ND@G catalyst.The present work paves a new way for designing highly dispersed and stable supported metal catalysts for DDH reactions.
