Methane(CH4),the predominant component of natural gas and shale gas,is regarded as a promising carbon feedstock for chemical synthesis[1].However,considering the extreme stability of CH4 molecules,it's quite chall...Methane(CH4),the predominant component of natural gas and shale gas,is regarded as a promising carbon feedstock for chemical synthesis[1].However,considering the extreme stability of CH4 molecules,it's quite challenging in simultaneously achieving high activity and selectivity for target products under mild conditions,especially when synthesizing high-value C2t chemicals such as ethanol[2].The conversion of methane to ethanol by photocatalysis is promising for achieving transformation under ambient temperature and pressure conditions.Currently,the apparent quantum efficiency(AQE)of solar-driven methane-to-ethanol conversion is generally below 0.5%[3,4].Furthermore,the stability of photocatalysts remains inadequate,offering substantial potential for further improvement.展开更多
CONSPECTUS:Methane(CH_(4)),which is the main component of natural gas,is an abundant and widely available carbon resource.However,CH_(4) has a low energy density of only 36 kJ L^(−1) under ambient conditions,which is ...CONSPECTUS:Methane(CH_(4)),which is the main component of natural gas,is an abundant and widely available carbon resource.However,CH_(4) has a low energy density of only 36 kJ L^(−1) under ambient conditions,which is significantly lower than that of gasoline(ca.34 MJ L^(−1)).The activation and catalytic conversion of CH_(4) into value-added chemicals[e.g.,methanol(CH3OH),which has an energy density of ca.17 MJ L^(−1)],can effectively lift its energy density.However,this conversion is highly challenging due to the inert nature of CH_(4),characterized by its strong C−H bonds and high stability.Consequently,the development of efficient materials that can optimize the binding and activation pathway of CH_(4) with control of product selectivity has attracted considerable recent interest.Metal−organic framework(MOF)materials have emerged as particularly attractive candidates for the development of efficient sorbents and heterogeneous catalysts due to their high porosity,low density,high surface area and structural versatility.These properties enable MOFs to act as effective platforms for the adsorption,binding and catalytic conversion of CH_(4) into valuable chemicals.Recent reports have highlighted MOFs as promising materials for these applications,leading to new insights into the structure−activity relationships that govern their performance in various systems.In this Account,we present analysis of state-of-the-art MOF-based sorbents and catalysts,particularly focusing on materials that incorporate well-defined active sites within confined space.The precise control of these active sites and their surrounding microenvironment is crucial as it directly influences the efficiency of CH_(4) activation and the selectivity of the resulting chemical products.Our discussion covers key reactions involving CH_(4),including its activation,selective oxidation of CH_(4) to CH3OH,dry reforming of CH_(4),nonoxidative coupling of CH_(4),and borylation of CH_(4).We analyze the role of active sites and their microenvironment in the binding and activation of CH_(4) using a wide range of experimental and computational studies,including neutron diffraction,inelastic neutron scattering,and electron paramagnetic resonance,solid-state nuclear magnetic resonance,infrared and X-ray absorption spectroscopies coupled to density functional theory calculations.In particular,neutron scattering has notable advantages in elucidating host−vip interactions and the mechanisms of the conversion and catalysis of CH_(4) and CD_(4).In addition to exploring current advances,the limitations and future direction of research in this area are also discussed.Key challenges include improvements in the stability,scalability,and performance of MOFs under practical conditions,as well as achieving higher selectivity and yields of targeted products.The ongoing development of MOFs and related materials holds great promise for the efficient and sustainable utilization of CH_(4),transforming it from a low-density energy source into a versatile precursor for a wide range of value-added chemicals.This Account summarizes the design and development of functional MOF and related materials for the adsorption and conversion of CH_(4).展开更多
Methane,as the main component of natural gas,is a key transitional fuel resource due to its abundance and relatively low carbon emissions,aligning with global carbon neutrality objectives[1].Traditional natural gas st...Methane,as the main component of natural gas,is a key transitional fuel resource due to its abundance and relatively low carbon emissions,aligning with global carbon neutrality objectives[1].Traditional natural gas storage methods,such as liquefied and compressed natural gas,require costly infrastructure and high-pressure conditions.Alternatively,adsorbed natural gas offers a safer,more cost-effective,and environmentally friendly solution by enhancing storage capacity at reduced pressures through the use of methane adsorbents[2].展开更多
基金the support from the National Natural Science Foundation of China(52202306)Program from Guangdong Introducing Innovative and Entrepreneurial Teams(2019ZT08L101 and RCTDPT-2020-001)+1 种基金Shenzhen Key Laboratory of Eco-materials and Renewable Energy(ZDSYS20200922160400001)the Provincial Talent Plan of Guangdong(2023TB0012).
文摘Methane(CH4),the predominant component of natural gas and shale gas,is regarded as a promising carbon feedstock for chemical synthesis[1].However,considering the extreme stability of CH4 molecules,it's quite challenging in simultaneously achieving high activity and selectivity for target products under mild conditions,especially when synthesizing high-value C2t chemicals such as ethanol[2].The conversion of methane to ethanol by photocatalysis is promising for achieving transformation under ambient temperature and pressure conditions.Currently,the apparent quantum efficiency(AQE)of solar-driven methane-to-ethanol conversion is generally below 0.5%[3,4].Furthermore,the stability of photocatalysts remains inadequate,offering substantial potential for further improvement.
基金EPSRC(EP/I011870,EP/V056409),Natural Science Foundation of ChinaPeking University,BNLMS+2 种基金the University of ManchesterUK Catalysis Hub(EP/R026939,EP/R026815,EP/R026645,EP/R027129)for fundingfunding from the European Research Council(ERC)under the European Union’s Horizon 2020 research and innovation programme(grant agreement No 742401,NANOCHEM).
文摘CONSPECTUS:Methane(CH_(4)),which is the main component of natural gas,is an abundant and widely available carbon resource.However,CH_(4) has a low energy density of only 36 kJ L^(−1) under ambient conditions,which is significantly lower than that of gasoline(ca.34 MJ L^(−1)).The activation and catalytic conversion of CH_(4) into value-added chemicals[e.g.,methanol(CH3OH),which has an energy density of ca.17 MJ L^(−1)],can effectively lift its energy density.However,this conversion is highly challenging due to the inert nature of CH_(4),characterized by its strong C−H bonds and high stability.Consequently,the development of efficient materials that can optimize the binding and activation pathway of CH_(4) with control of product selectivity has attracted considerable recent interest.Metal−organic framework(MOF)materials have emerged as particularly attractive candidates for the development of efficient sorbents and heterogeneous catalysts due to their high porosity,low density,high surface area and structural versatility.These properties enable MOFs to act as effective platforms for the adsorption,binding and catalytic conversion of CH_(4) into valuable chemicals.Recent reports have highlighted MOFs as promising materials for these applications,leading to new insights into the structure−activity relationships that govern their performance in various systems.In this Account,we present analysis of state-of-the-art MOF-based sorbents and catalysts,particularly focusing on materials that incorporate well-defined active sites within confined space.The precise control of these active sites and their surrounding microenvironment is crucial as it directly influences the efficiency of CH_(4) activation and the selectivity of the resulting chemical products.Our discussion covers key reactions involving CH_(4),including its activation,selective oxidation of CH_(4) to CH3OH,dry reforming of CH_(4),nonoxidative coupling of CH_(4),and borylation of CH_(4).We analyze the role of active sites and their microenvironment in the binding and activation of CH_(4) using a wide range of experimental and computational studies,including neutron diffraction,inelastic neutron scattering,and electron paramagnetic resonance,solid-state nuclear magnetic resonance,infrared and X-ray absorption spectroscopies coupled to density functional theory calculations.In particular,neutron scattering has notable advantages in elucidating host−vip interactions and the mechanisms of the conversion and catalysis of CH_(4) and CD_(4).In addition to exploring current advances,the limitations and future direction of research in this area are also discussed.Key challenges include improvements in the stability,scalability,and performance of MOFs under practical conditions,as well as achieving higher selectivity and yields of targeted products.The ongoing development of MOFs and related materials holds great promise for the efficient and sustainable utilization of CH_(4),transforming it from a low-density energy source into a versatile precursor for a wide range of value-added chemicals.This Account summarizes the design and development of functional MOF and related materials for the adsorption and conversion of CH_(4).
文摘Methane,as the main component of natural gas,is a key transitional fuel resource due to its abundance and relatively low carbon emissions,aligning with global carbon neutrality objectives[1].Traditional natural gas storage methods,such as liquefied and compressed natural gas,require costly infrastructure and high-pressure conditions.Alternatively,adsorbed natural gas offers a safer,more cost-effective,and environmentally friendly solution by enhancing storage capacity at reduced pressures through the use of methane adsorbents[2].
