Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction(NO_(3)RR)is crucial for the enhancement of reaction efficiency.However,it remains a great challenge to regulate the reaction int...Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction(NO_(3)RR)is crucial for the enhancement of reaction efficiency.However,it remains a great challenge to regulate the reaction intermediates through active site manipulation on the surface of the catalyst.Here,a family of n%-Co_(3)O_(4)/SiC(n=5,8,12,20)catalysts with a delicate percentage of Co^(2+)and Co^(3+)were prepared for NO_(3)RR.We found that Co^(3+)primarily acts as the active site for NO_(3)^(−)reduction to NO_(2)^(−),while Co^(2+)is responsible for the conversion of NO_(2)^(−)to NH_(3).Moreover,the conversion of these intermediates over the active sites is autonomous and separately controllable.Both processes synergistically accomplish the reduction of nitrate ions to synthesize ammonia.Combining the experimental studies and density functional theory(DFT)calculations,it is discovered the pathway(^(*)NHO→^(*)NHOH→^(*)NH_(2)OH→^(*)NH_(2)→^(*)NH_(3))is more favorable due to the lowerΔG value(0.25 eV)for the rate-limiting step(^(*)NO→^(*)NHO).The NH_(3)yield rate of 8%-Co_(3)O_(4)/SiC reached 1.08 mmol/(cm^(2)h)with a Faradaic efficiency of 96.4%at−0.89 V versus the reversible hydrogen electrode(RHE),surpassing those of most reported non-noble NO_(3)RR catalysts.This strategy not only provides an efficient catalyst for NO_(3)RR but also serves as an illustrative model for the regulation of multi-step reaction intermediates through the design of distinct active sites,thereby presenting a new approach to enhance the efficiency of intricate reactions.展开更多
High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface...High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.展开更多
It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxide...It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxides often involves introducing multiple elements with different properties,thereby providing outstanding bifunctional catalytic activity for OER/ORR.Nevertheless,the possible underlying catalytic pathways and potential interactions between various components are still poorly understood.This paper presents an excellent medium-entropy perovskite oxide,Sr(FeCoNiMo)_(1/4)O_(3−δ)(lower overpotential of 301 mV at 10 mA cm^(−2)).Zinc-air batteries employing it as a cathode catalyst demonstrate excellent round-trip efficiency(62%).By combining theoretical calculation with experiments,we aim to establish the link between the electronic structure of perovskite oxides with different elemental compositions and their OER mechanism.Research reveals that the conformational entropy strategy can simultaneously shift the O 2p-band center and metal d-band center of perovskite oxide towards the vicinity of the Fermi energy level,thereby triggering a more favorable lattice oxygen-participated mechanism(LOM)during the OER process.The outcomes of this work provide crucial insights into the role of conformational entropy strategies in oxygen catalysis and offer potential avenues for constructing efficient and stable electrocatalysts.展开更多
基金financially supported by the National Key Research and Development Program of China (2018YFA0209404)the Fundamental Research Funds for the Central Universities (DUT22LAB601)
文摘Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction(NO_(3)RR)is crucial for the enhancement of reaction efficiency.However,it remains a great challenge to regulate the reaction intermediates through active site manipulation on the surface of the catalyst.Here,a family of n%-Co_(3)O_(4)/SiC(n=5,8,12,20)catalysts with a delicate percentage of Co^(2+)and Co^(3+)were prepared for NO_(3)RR.We found that Co^(3+)primarily acts as the active site for NO_(3)^(−)reduction to NO_(2)^(−),while Co^(2+)is responsible for the conversion of NO_(2)^(−)to NH_(3).Moreover,the conversion of these intermediates over the active sites is autonomous and separately controllable.Both processes synergistically accomplish the reduction of nitrate ions to synthesize ammonia.Combining the experimental studies and density functional theory(DFT)calculations,it is discovered the pathway(^(*)NHO→^(*)NHOH→^(*)NH_(2)OH→^(*)NH_(2)→^(*)NH_(3))is more favorable due to the lowerΔG value(0.25 eV)for the rate-limiting step(^(*)NO→^(*)NHO).The NH_(3)yield rate of 8%-Co_(3)O_(4)/SiC reached 1.08 mmol/(cm^(2)h)with a Faradaic efficiency of 96.4%at−0.89 V versus the reversible hydrogen electrode(RHE),surpassing those of most reported non-noble NO_(3)RR catalysts.This strategy not only provides an efficient catalyst for NO_(3)RR but also serves as an illustrative model for the regulation of multi-step reaction intermediates through the design of distinct active sites,thereby presenting a new approach to enhance the efficiency of intricate reactions.
基金supported by the National Key R&D Program of China(Grant No.2023YFB2503900)the National Natural Science Foundation of China(Grant No.52372203)+1 种基金the National Natural Science Foundation of China(Grant No.52202259)the Shandong Province Natural Science Foundation(ZR2022QE093).
文摘High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.
基金the financial support from the National Natural Science Foundation of China (51872067 and 21773048)
文摘It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxides often involves introducing multiple elements with different properties,thereby providing outstanding bifunctional catalytic activity for OER/ORR.Nevertheless,the possible underlying catalytic pathways and potential interactions between various components are still poorly understood.This paper presents an excellent medium-entropy perovskite oxide,Sr(FeCoNiMo)_(1/4)O_(3−δ)(lower overpotential of 301 mV at 10 mA cm^(−2)).Zinc-air batteries employing it as a cathode catalyst demonstrate excellent round-trip efficiency(62%).By combining theoretical calculation with experiments,we aim to establish the link between the electronic structure of perovskite oxides with different elemental compositions and their OER mechanism.Research reveals that the conformational entropy strategy can simultaneously shift the O 2p-band center and metal d-band center of perovskite oxide towards the vicinity of the Fermi energy level,thereby triggering a more favorable lattice oxygen-participated mechanism(LOM)during the OER process.The outcomes of this work provide crucial insights into the role of conformational entropy strategies in oxygen catalysis and offer potential avenues for constructing efficient and stable electrocatalysts.
