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
In the domain of acidic water splitting,designing bifunctional catalysts that marry high activity with enduring stability is a formidable challenge.Herein,we have constructed platinum-containing ruthenium oxide nanopa...In the domain of acidic water splitting,designing bifunctional catalysts that marry high activity with enduring stability is a formidable challenge.Herein,we have constructed platinum-containing ruthenium oxide nanoparticles(Pt@RuO_(x)NPs)to achieve excellent overall water splitting performance in acidic electrolytes.Pt@RuO_(x)NPs demonstrate exceptional catalytic activity for both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in acidic seawater,requiring overpotentials of only 20 and 157 mV,respectively to achieve a current density of 10 mA cm^(-2).Furthermore,in 0.5 M H_(2)SO_(4),this catalyst exhibits high HER(19 mV)and OER(236 mV)catalytic activities.The two-electrode water splitting system composed of bifunctional Pt@RuO_(x)NPs requires cell voltages of only 1.442 and 1.465 V to deliver a current density of 10 mA cm^(-2)in acidic seawater and 0.5 M H_(2)SO_(4).Remarkably,this catalyst displays remarkable stability in the water splitting process.It is shown that the introduction of Pt could augment oxygen vacancies and enhance catalytic activity significantly.The synergy between Pt and Ru further contributes to the improved performance.Additionally,we have observed that acidic seawater holds distinct advantages for acidic water splitting,along with a thorough exploration of the relationship between Cl^(-)concentration and catalytic performance.This study not only provides a strategy to improve the catalytic activity and stability of ruthenium-based catalysts for water splitting in acidic environments,but also unveils the promoting effect of Cl^(-)on the catalytic activity in acidic water splitting.展开更多
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supported by the National Natural Science Foundation of China(51971157 and 22075211)Shenzhen Science and Technology Program(JCYJ20210324115412035,JCYJ20210324123202008,JCYJ20210324122803009 and ZDSYS20210813095534001)Guangdong Foundation for Basic and Applied Basic Research Program(2021A1515110880)
文摘In the domain of acidic water splitting,designing bifunctional catalysts that marry high activity with enduring stability is a formidable challenge.Herein,we have constructed platinum-containing ruthenium oxide nanoparticles(Pt@RuO_(x)NPs)to achieve excellent overall water splitting performance in acidic electrolytes.Pt@RuO_(x)NPs demonstrate exceptional catalytic activity for both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in acidic seawater,requiring overpotentials of only 20 and 157 mV,respectively to achieve a current density of 10 mA cm^(-2).Furthermore,in 0.5 M H_(2)SO_(4),this catalyst exhibits high HER(19 mV)and OER(236 mV)catalytic activities.The two-electrode water splitting system composed of bifunctional Pt@RuO_(x)NPs requires cell voltages of only 1.442 and 1.465 V to deliver a current density of 10 mA cm^(-2)in acidic seawater and 0.5 M H_(2)SO_(4).Remarkably,this catalyst displays remarkable stability in the water splitting process.It is shown that the introduction of Pt could augment oxygen vacancies and enhance catalytic activity significantly.The synergy between Pt and Ru further contributes to the improved performance.Additionally,we have observed that acidic seawater holds distinct advantages for acidic water splitting,along with a thorough exploration of the relationship between Cl^(-)concentration and catalytic performance.This study not only provides a strategy to improve the catalytic activity and stability of ruthenium-based catalysts for water splitting in acidic environments,but also unveils the promoting effect of Cl^(-)on the catalytic activity in acidic water splitting.
