The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster mode...The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster model including the Mo-edge,the S-edge,and the rarely mentioned corner site.It was found that the adsorption of quinoline is stronger than that of benzothiophene at all the active sites.It indicated the origin of the inhibition effect of nitrogen compounds on HDS.And Ni atoms located around Mo-edge and corner site exhibit higher adsorption selectivity to sulfur compounds than the nitrogen ones.It means that the increase in Ni-promoting effect may weaken the inhibition effect of nitrogen compounds on HDS.展开更多
Developing efficient and robust oxygen evolution reaction(OER)catalysts in seawater is important for green hydrogen generation but remains a significant challenge.Herein,we report a hierarchical core-shell OER electro...Developing efficient and robust oxygen evolution reaction(OER)catalysts in seawater is important for green hydrogen generation but remains a significant challenge.Herein,we report a hierarchical core-shell OER electrocatalyst consisting of NiFe-layered double hydroxide nanosheets uniformly coated on a NiMoS_(x)microcolumn supported on Ni foam(NiMoS_(x)@NiFe-LDH/NF).展开更多
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically slug...Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.展开更多
Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen ev...Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen evolution reaction(HER)kinetics of commercial catalysts.To overcome this limitation,this study focuses on the development of a highly efficient electrocatalyst for alkaline HER.Ni-based intermetallic compounds exhibit remarkable catalytic activity for HER,with the NiMo alloy being among the most active catalysts in alkaline environments.Here,we designed and fabricated self-supported multiscale porous NiZn/NiMo intermetallic compounds on a metal foam substrate using a versatile dealloying method.The resulting electrode exhibits excellent HER activity,achieving an overpotential of just 204 mV at 1000 mA/cm^(2),and dem-onstrates robust long-term catalytic stability,maintaining performance at 100 mA/cm^(2) for 400 h in an alkaline electrolyte.Thesefindings underscore the potential of nanosized intermetallic compounds fabricated via a dealloying approach to deliver exceptional catalytic performance for alkaline water electrolysis.展开更多
NiMo catalyst exhibits excellent catalytic performance in the electrooxidation of 5-hydroxymethylfurfural(HMF)to produce high-value 2,5-furandicarboxylic acid(FDCA).Although metallic nickel is known to undergo reconst...NiMo catalyst exhibits excellent catalytic performance in the electrooxidation of 5-hydroxymethylfurfural(HMF)to produce high-value 2,5-furandicarboxylic acid(FDCA).Although metallic nickel is known to undergo reconstruction into high-valent species during the reaction,the dynamic evolution of molybdenum components in NiMo catalyst and their mechanistic roles in catalytic reaction remain unclear.In this study,the structural evolution of NiMo alloy during HMF electrooxidation is systematically investigated.Operando analyses reveal that under anodic polarization,molybdenum undergoes oxidative dissolution in the form of MoO_(4)^(2-),concurrently driving the generation of high-valent Ni^(3+)species.Meanwhile,the dissolved MoO_(4)^(2-)re-adsorbs on the catalyst surface,forming a unique interfacial structure with Ni^(3+).Electrochemical results demonstrate that this surface structure facilitates a synergistic effect between the MoO_(4)^(2-)and high-valent Ni^(3+),enhancing the adsorption and activation of HMF molecules.Therefore,the NiMo alloy exhibits excellent catalytic performance,with a high FDCA selectivity of 99.0%.This study provides new insights into the relationship between the catalyst reconstruction process and enhancement of catalytic performance.展开更多
基金We gratefully acknowledge the support from the National Key Research and Development Plan(Grant No.2017YFB0306603)China Petrochemical Corporation funding(Sinopec Group,No.117006)on this work.
文摘The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster model including the Mo-edge,the S-edge,and the rarely mentioned corner site.It was found that the adsorption of quinoline is stronger than that of benzothiophene at all the active sites.It indicated the origin of the inhibition effect of nitrogen compounds on HDS.And Ni atoms located around Mo-edge and corner site exhibit higher adsorption selectivity to sulfur compounds than the nitrogen ones.It means that the increase in Ni-promoting effect may weaken the inhibition effect of nitrogen compounds on HDS.
基金supported by the Free Exploration Project of Frontier Technology for Laoshan Laboratory(No.16-02)the National Natural Science Foundation of China(No.22072015).
文摘Developing efficient and robust oxygen evolution reaction(OER)catalysts in seawater is important for green hydrogen generation but remains a significant challenge.Herein,we report a hierarchical core-shell OER electrocatalyst consisting of NiFe-layered double hydroxide nanosheets uniformly coated on a NiMoS_(x)microcolumn supported on Ni foam(NiMoS_(x)@NiFe-LDH/NF).
基金financially supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008)the Natural Science Foundation of Jilin Province of China(No.20240101098JC)the National Natural Science Foundation of China(No.22469002)。
文摘Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
基金Taishan Scholar Project of Shandong Province(No.tsqn202306226)Natural Science Foundation of Shandong Prov-ince(No.ZR2023ME155)+1 种基金The project of“20 Items of University”of Jinan(No.202228046)Luzhou Municipal Science and Technol-ogy Plan Project(Nos.2024JYJ016 and 2024JYJ018).
文摘Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen evolution reaction(HER)kinetics of commercial catalysts.To overcome this limitation,this study focuses on the development of a highly efficient electrocatalyst for alkaline HER.Ni-based intermetallic compounds exhibit remarkable catalytic activity for HER,with the NiMo alloy being among the most active catalysts in alkaline environments.Here,we designed and fabricated self-supported multiscale porous NiZn/NiMo intermetallic compounds on a metal foam substrate using a versatile dealloying method.The resulting electrode exhibits excellent HER activity,achieving an overpotential of just 204 mV at 1000 mA/cm^(2),and dem-onstrates robust long-term catalytic stability,maintaining performance at 100 mA/cm^(2) for 400 h in an alkaline electrolyte.Thesefindings underscore the potential of nanosized intermetallic compounds fabricated via a dealloying approach to deliver exceptional catalytic performance for alkaline water electrolysis.
基金supported by the Natural Science Foundation of Guangxi Zhuang(2022JJD120011)the National Natural Science Foundation of China(22479031,22162004)the Project for Enhancing Young and Middle-aged Teacher's Research Basis Ability in Colleges of Guangxi(2025KY0040).
文摘NiMo catalyst exhibits excellent catalytic performance in the electrooxidation of 5-hydroxymethylfurfural(HMF)to produce high-value 2,5-furandicarboxylic acid(FDCA).Although metallic nickel is known to undergo reconstruction into high-valent species during the reaction,the dynamic evolution of molybdenum components in NiMo catalyst and their mechanistic roles in catalytic reaction remain unclear.In this study,the structural evolution of NiMo alloy during HMF electrooxidation is systematically investigated.Operando analyses reveal that under anodic polarization,molybdenum undergoes oxidative dissolution in the form of MoO_(4)^(2-),concurrently driving the generation of high-valent Ni^(3+)species.Meanwhile,the dissolved MoO_(4)^(2-)re-adsorbs on the catalyst surface,forming a unique interfacial structure with Ni^(3+).Electrochemical results demonstrate that this surface structure facilitates a synergistic effect between the MoO_(4)^(2-)and high-valent Ni^(3+),enhancing the adsorption and activation of HMF molecules.Therefore,the NiMo alloy exhibits excellent catalytic performance,with a high FDCA selectivity of 99.0%.This study provides new insights into the relationship between the catalyst reconstruction process and enhancement of catalytic performance.
