Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/C...Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis(30 s).The OH-from rapid surface hydrolysis of Co_(2)P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site,which may bring out better synergistic effect for alkaline HER.Moreover,the covering of CoRuOH can improve the stability of Co_(2)P for HER.When drives at 100 mA/cm^(2),it only requires overpotential of 81 mV in 1.0 mol/L KOH(25℃).Even at higher current density(1000 mA/cm^(2)),CoRuOH/Co_(2)P/CF can also operate stability for at least 100 h.When coupling with NiFe-LDH/IF in a two-electrode system,the voltage of NiFe-LDH/IF(+)||CoRuOH/Co_(2)P/CF(-)at 1000 mA/cm^(2)is merely 1.77 V with 100 h,demonstrating great potential for water splitting.The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.展开更多
The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction wa...The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction was a major challenge.Here,we propose a strategy to accelerate surface water oxidation through the fabrication spatially separated double active sites.FeCoPi/Bi_(4)NbO_(8)Cl-OVs photocatalyst with spatially separated double active site was prepared by hydrogen reduction photoanode deposition method.Due to the high matching of the spatial loading positions of FeCoPi and OVs with the photogenerated charge distribution of Bi_(4)NbO_(8)Cl and corresponding reaction mechanisms of substrate,the FeCoPi and OVs on the(001)and(010)crystal planes of Bi_(4)NbO_(8)Cl photocatalyst provided surface active site for water oxidation reaction and electron shuttle reaction(Fe^(3+)/Fe^(2+)),respectively.Under visible light irradiation,the evolution O_(2)rate of FeCoPi/Bi_(4)NbO_(8)Cl OVs was 16.8μmol h^(-1),as 32.9 times as Bi_(4)NbO_(8)Cl.Furthermore,a hydrogen evolution co-catalyst PtRu@Cr_(2)O_(3)was prepared by sequential photodeposition method.Due to the introduction of Ru,the Schottky barrier between PbTiO_(3)and Pt was effectively reduced,which promoted the transfer of photogenerated electrons to PtRu@Cr_(2)O_(3)thermodynamically,the evolution H_(2)rate on PtRu@Cr_(2)O_(3)/PbTiO_(3)increased to 664.8 times.On based of the synchronous enhancement of the water oxidation performance on FeCoPi/Bi_(4)NbO_(8)Cl-OVs and water reduction performance on PtRu@Cr_(2)O_(3)/PbTiO_(3),a novel Z-Scheme photocatalytic overall water splitting system(FeCoPi/Bi_(4)NbO_(8)Cl-OVs)mediated by Fe^(3+)/Fe^(2+)had successfully constructed.Under visible light irradiation,the evolution rates of H_(2)and O_(2)were 2.5 and 1.3μmol h^(-1),respectively.This work can provide some reference for the design of active site and the controllable synthesis of OVs spatial position.On the other hand,the hydrogen evolution co catalyst(PtRu@Cr_(2)O_(3))and the co catalyst FeCoPi for oxygen evolution contributed to the construction of an overall water splitting system.展开更多
The development of high-performance,low-cost bifunctional catalysts with long-term stability for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is one of the most critical challenges for the large...The development of high-performance,low-cost bifunctional catalysts with long-term stability for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is one of the most critical challenges for the large-scale application of metal-air batteries.Herein,we report an advanced nitrogen-doped mesoporous carbon(NMC)composite(NiCo2O4/CoNx-NMC)formed from a mixture of Co-and Ni-hydroxide-infiltrated phenolic resin and melamine resin.This composite exhibits superior electrocatalytic activity,stability,and selectivity for the ORR and OER.The activity parameter(DE),which is an indicator of the overall catalytic activity of bifunctional catalysts,was 0.76 V for NiCo2O4/CoNx-NMC.Therefore,catalyst outperforms the majority of previously reported non-precious metal-based bifunctional electrocatalysts.The remarkable ultra-high catalytic performance of NiCo2O4/CoNx-NMC for the ORR and OER can be attributed to the presence of different active sites of the CoNx structure and the formation of NiCo2O4 with the spinel structure,which was obtained by a stepwise pyrolysis process.This synthesis strategy opens a new avenue for the rational design of highly active bifunctional electrocatalysts.展开更多
To improve the electrochemical activity of S electrodes in Li-S batteries,the synergistic electrocatalysis mechanism of Co_(0.4)Ni_(1.6)P with Ni and Co bimetal interactions is clarified.The alternating crystal struct...To improve the electrochemical activity of S electrodes in Li-S batteries,the synergistic electrocatalysis mechanism of Co_(0.4)Ni_(1.6)P with Ni and Co bimetal interactions is clarified.The alternating crystal structure of Co and Ni regulates the adsorption and decomposition energy of Co_(0.4)Ni_(1.6)P to polysulfides and has the bidirectional catalysis for the Li_(2)S_(1-2)deposition/decomposition process.Co_(0.4)Ni_(1.6)P can promote the breaking of the S-S bond of Li_(2)S_(4) and decrease the decomposition energy barrier of Li_(2)S.This regulation accelerates the discharge/charge reaction between S,polysulfides,and Li_(2)S and improves the kinetics of the S electrodes.The 1st,100^(th),and 200^(th) discharge capacity densities at 0.1 mA cm^(-2) of the S electrodes with a high sulfur loading were 1,405,987.2,and 828.4 m Ah gS^(-1),respectively.The bidirectional catalytic mechanism is a novel idea for improving the electrochemical performance of Li-S batteries.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.52174283 and 52274308)。
文摘Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis(30 s).The OH-from rapid surface hydrolysis of Co_(2)P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site,which may bring out better synergistic effect for alkaline HER.Moreover,the covering of CoRuOH can improve the stability of Co_(2)P for HER.When drives at 100 mA/cm^(2),it only requires overpotential of 81 mV in 1.0 mol/L KOH(25℃).Even at higher current density(1000 mA/cm^(2)),CoRuOH/Co_(2)P/CF can also operate stability for at least 100 h.When coupling with NiFe-LDH/IF in a two-electrode system,the voltage of NiFe-LDH/IF(+)||CoRuOH/Co_(2)P/CF(-)at 1000 mA/cm^(2)is merely 1.77 V with 100 h,demonstrating great potential for water splitting.The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.
基金supported by National Natural Science Foundation of China(22369022)Technology Innovation Leading Program of Shaanxi(2022QFY07-03)。
文摘The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction was a major challenge.Here,we propose a strategy to accelerate surface water oxidation through the fabrication spatially separated double active sites.FeCoPi/Bi_(4)NbO_(8)Cl-OVs photocatalyst with spatially separated double active site was prepared by hydrogen reduction photoanode deposition method.Due to the high matching of the spatial loading positions of FeCoPi and OVs with the photogenerated charge distribution of Bi_(4)NbO_(8)Cl and corresponding reaction mechanisms of substrate,the FeCoPi and OVs on the(001)and(010)crystal planes of Bi_(4)NbO_(8)Cl photocatalyst provided surface active site for water oxidation reaction and electron shuttle reaction(Fe^(3+)/Fe^(2+)),respectively.Under visible light irradiation,the evolution O_(2)rate of FeCoPi/Bi_(4)NbO_(8)Cl OVs was 16.8μmol h^(-1),as 32.9 times as Bi_(4)NbO_(8)Cl.Furthermore,a hydrogen evolution co-catalyst PtRu@Cr_(2)O_(3)was prepared by sequential photodeposition method.Due to the introduction of Ru,the Schottky barrier between PbTiO_(3)and Pt was effectively reduced,which promoted the transfer of photogenerated electrons to PtRu@Cr_(2)O_(3)thermodynamically,the evolution H_(2)rate on PtRu@Cr_(2)O_(3)/PbTiO_(3)increased to 664.8 times.On based of the synchronous enhancement of the water oxidation performance on FeCoPi/Bi_(4)NbO_(8)Cl-OVs and water reduction performance on PtRu@Cr_(2)O_(3)/PbTiO_(3),a novel Z-Scheme photocatalytic overall water splitting system(FeCoPi/Bi_(4)NbO_(8)Cl-OVs)mediated by Fe^(3+)/Fe^(2+)had successfully constructed.Under visible light irradiation,the evolution rates of H_(2)and O_(2)were 2.5 and 1.3μmol h^(-1),respectively.This work can provide some reference for the design of active site and the controllable synthesis of OVs spatial position.On the other hand,the hydrogen evolution co catalyst(PtRu@Cr_(2)O_(3))and the co catalyst FeCoPi for oxygen evolution contributed to the construction of an overall water splitting system.
基金financially supported by the National Natural Science Foundation of China(No.21677171)the West Light Foundation of Chinese Academy of Sciences(No.2016-YJRC-1)。
文摘The development of high-performance,low-cost bifunctional catalysts with long-term stability for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is one of the most critical challenges for the large-scale application of metal-air batteries.Herein,we report an advanced nitrogen-doped mesoporous carbon(NMC)composite(NiCo2O4/CoNx-NMC)formed from a mixture of Co-and Ni-hydroxide-infiltrated phenolic resin and melamine resin.This composite exhibits superior electrocatalytic activity,stability,and selectivity for the ORR and OER.The activity parameter(DE),which is an indicator of the overall catalytic activity of bifunctional catalysts,was 0.76 V for NiCo2O4/CoNx-NMC.Therefore,catalyst outperforms the majority of previously reported non-precious metal-based bifunctional electrocatalysts.The remarkable ultra-high catalytic performance of NiCo2O4/CoNx-NMC for the ORR and OER can be attributed to the presence of different active sites of the CoNx structure and the formation of NiCo2O4 with the spinel structure,which was obtained by a stepwise pyrolysis process.This synthesis strategy opens a new avenue for the rational design of highly active bifunctional electrocatalysts.
文摘To improve the electrochemical activity of S electrodes in Li-S batteries,the synergistic electrocatalysis mechanism of Co_(0.4)Ni_(1.6)P with Ni and Co bimetal interactions is clarified.The alternating crystal structure of Co and Ni regulates the adsorption and decomposition energy of Co_(0.4)Ni_(1.6)P to polysulfides and has the bidirectional catalysis for the Li_(2)S_(1-2)deposition/decomposition process.Co_(0.4)Ni_(1.6)P can promote the breaking of the S-S bond of Li_(2)S_(4) and decrease the decomposition energy barrier of Li_(2)S.This regulation accelerates the discharge/charge reaction between S,polysulfides,and Li_(2)S and improves the kinetics of the S electrodes.The 1st,100^(th),and 200^(th) discharge capacity densities at 0.1 mA cm^(-2) of the S electrodes with a high sulfur loading were 1,405,987.2,and 828.4 m Ah gS^(-1),respectively.The bidirectional catalytic mechanism is a novel idea for improving the electrochemical performance of Li-S batteries.