For treatment of sulfion-containing wastewater,coupling the electrochemical sulfion oxidation reaction(SOR)with hydrogen evolution reaction(HER)can be an ideal way for sulfur and H_(2)resources recovery.Herein,we synt...For treatment of sulfion-containing wastewater,coupling the electrochemical sulfion oxidation reaction(SOR)with hydrogen evolution reaction(HER)can be an ideal way for sulfur and H_(2)resources recovery.Herein,we synthesize a metal-modified carbon nanotube arrays electrode(Co@N-CNTs/CC)for SOR and HER.This electrode has excellent performance for SOR and HER attributed to the unique array structure.It can achieve 99.36 mA/cm^(2)at 0.6 V for SOR,and 10 mA/cm^(2)at 0.067 V for HER.Density functional theory calculations verify that metal modification is able to regulate the electronic structure of carbon nanotube,which is able to optimize the adsorption of intermediates.Employed Co@N-CNTs/CC as bifunctional elec-trodes to establish a hybrid electrolytic cell can reduce about 67%of energy consumption compared with the traditional water splitting electrolytic cell.Finally,the hybrid electrolytic cell is used to treat actual sulfion-containing wastewater,achieving the sulfur yield of 30 mg h^(−1)cm^(−2)and the hydrogen production of 0.64 mL/min.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
Herein,we propose a simple and rapid approach for synthesizing a CuS/Ru composite that serves as a bifunctional electrocatalyst to promote hydrogen production and concurrently convert sulfion into a value-added sulfur...Herein,we propose a simple and rapid approach for synthesizing a CuS/Ru composite that serves as a bifunctional electrocatalyst to promote hydrogen production and concurrently convert sulfion into a value-added sulfur product.This composite comprises Ru nanoclusters supported on the CuS nanostructure,achieved through simple pulsed laser irradiation in liquid approach.The optimized CuS/Ru-30 electrocatalyst demonstrates remarkable bifunctional electrocatalytic activity,exhibiting a negligible working potential of 0.28 V(vs.RHE)for the anodic sulfion oxidation reaction(SOR)and a minimal overpotential of 182 m V for cathodic hydrogen evolution reaction(HER)to achieve 10 mA cm^(-2)of current density.Moreover,the Cu S/Ru-30 electrocatalyst shows exceptional selectivity for converting sulfion into valuable sulfur during anodic oxidation reactions.Remarkably,in a two-electrode electrolyzer system utilizing Cu S/Ru-30 as both the anode and cathode,the SOR+HER coupled water electrolysis system demands only 0.52 V to reach 10 mA cm^(-2),which is considerably lesser compared to the OER+HER coupled water electrolysis(1.85 V).The experimental results and density function theory(DFT)calculations reveal that the strong electron interaction between CuS and Ru nanoclusters generates a built-in electric field,greatly enhancing electron transfer efficiency.This significantly boosts the HER performance and facilitates the adsorption and production of sulfur intermediates.This study presents a rapid and simple strategy for synthesizing a dual-functional catalyst suitable for low-voltage hydrogen generation while facilitating the recovery of valuable sulfur sources.展开更多
The sulfion oxidation reaction(SOR)has enormous potential in replacing slow kinetic oxygen evolution reactions and treating sulfur-containing wastewater.However,the sulfur aggregation generated by SOR will lead to a d...The sulfion oxidation reaction(SOR)has enormous potential in replacing slow kinetic oxygen evolution reactions and treating sulfur-containing wastewater.However,the sulfur aggregation generated by SOR will lead to a decline in SOR activity.Herein,an electrospinning-carbonization-vulcanization technique is introduced to fabricate Mo-NiS_(2)-co-embedded carbon nanofibers(Mo-NiS_(2)/CNFs).The integration of molybdenum promotes sulfophobicity of Mo-NiS_(2)/CNFs,and can thus effectively prevent its activity from being deactivated by sulfur deposition on the electrode surface during SOR,thereby improving catalytic activity and long-term stability.In particular,Mo-NiS_(2)/CNFs showed a distinguished durability at 100 m A cm^(-2)at least 100 h.In-situ Raman spectra tracked the evolution and oxidation conversion of S^(2-)to short-chain polysulfides(S_(2)^(2-)–S_(4)^(2-)),ultimately to valueadded S8.Density functional theory calculations unveiled that the introduction of Mo efficiently regulated the d-band center of NiS_(2),reduced the energy barrier in the rate-determining step from S_(2)^(2-)to S32-and the Gibbs free energy of H*adsorption,and thereby significantly promoted SOR and hydrogen evolution reaction(HER).Mo-NiS_(2)/CNFs-based anion exchange membrane water electrolyzer for HER and SOR achieved a current density of 500 m Acm^(-2)at 1.78 V for continuous H_(2)and S8productions.Such a coupling system performed an ultra-low power consumption of 2.127 kW hm^(-3)H_(2)at 500 m A cm^(-2),showing an energysaving hydrogen production and high desulfurization ability for environmental protection and remediation.展开更多
基金supported by Natural Science Foundation of Shandong Province(Nos.ZR2022QE076,ZR2021JQ15,ZR2019YQ20)the National Natural Science Foundation of China(Nos.52002145,52202092,51972147,52022037)Taishan Scholars Project Special Funds(No.tsqn201812083).
文摘For treatment of sulfion-containing wastewater,coupling the electrochemical sulfion oxidation reaction(SOR)with hydrogen evolution reaction(HER)can be an ideal way for sulfur and H_(2)resources recovery.Herein,we synthesize a metal-modified carbon nanotube arrays electrode(Co@N-CNTs/CC)for SOR and HER.This electrode has excellent performance for SOR and HER attributed to the unique array structure.It can achieve 99.36 mA/cm^(2)at 0.6 V for SOR,and 10 mA/cm^(2)at 0.067 V for HER.Density functional theory calculations verify that metal modification is able to regulate the electronic structure of carbon nanotube,which is able to optimize the adsorption of intermediates.Employed Co@N-CNTs/CC as bifunctional elec-trodes to establish a hybrid electrolytic cell can reduce about 67%of energy consumption compared with the traditional water splitting electrolytic cell.Finally,the hybrid electrolytic cell is used to treat actual sulfion-containing wastewater,achieving the sulfur yield of 30 mg h^(−1)cm^(−2)and the hydrogen production of 0.64 mL/min.
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 Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(No.2019R1A6C1010042)the financial support from the National Research Foundation of Korea(NRF)(2022R1A2C2010686,2022R1A4A3033528,2021R1C1C2010726)。
文摘Herein,we propose a simple and rapid approach for synthesizing a CuS/Ru composite that serves as a bifunctional electrocatalyst to promote hydrogen production and concurrently convert sulfion into a value-added sulfur product.This composite comprises Ru nanoclusters supported on the CuS nanostructure,achieved through simple pulsed laser irradiation in liquid approach.The optimized CuS/Ru-30 electrocatalyst demonstrates remarkable bifunctional electrocatalytic activity,exhibiting a negligible working potential of 0.28 V(vs.RHE)for the anodic sulfion oxidation reaction(SOR)and a minimal overpotential of 182 m V for cathodic hydrogen evolution reaction(HER)to achieve 10 mA cm^(-2)of current density.Moreover,the Cu S/Ru-30 electrocatalyst shows exceptional selectivity for converting sulfion into valuable sulfur during anodic oxidation reactions.Remarkably,in a two-electrode electrolyzer system utilizing Cu S/Ru-30 as both the anode and cathode,the SOR+HER coupled water electrolysis system demands only 0.52 V to reach 10 mA cm^(-2),which is considerably lesser compared to the OER+HER coupled water electrolysis(1.85 V).The experimental results and density function theory(DFT)calculations reveal that the strong electron interaction between CuS and Ru nanoclusters generates a built-in electric field,greatly enhancing electron transfer efficiency.This significantly boosts the HER performance and facilitates the adsorption and production of sulfur intermediates.This study presents a rapid and simple strategy for synthesizing a dual-functional catalyst suitable for low-voltage hydrogen generation while facilitating the recovery of valuable sulfur sources.
基金supported by the National Natural Science Foundation of China(22068037,22162025)the Key Joint Project between Departments and Municipalities of Shaanxi Province(2022GD-TSLD-68)。
文摘The sulfion oxidation reaction(SOR)has enormous potential in replacing slow kinetic oxygen evolution reactions and treating sulfur-containing wastewater.However,the sulfur aggregation generated by SOR will lead to a decline in SOR activity.Herein,an electrospinning-carbonization-vulcanization technique is introduced to fabricate Mo-NiS_(2)-co-embedded carbon nanofibers(Mo-NiS_(2)/CNFs).The integration of molybdenum promotes sulfophobicity of Mo-NiS_(2)/CNFs,and can thus effectively prevent its activity from being deactivated by sulfur deposition on the electrode surface during SOR,thereby improving catalytic activity and long-term stability.In particular,Mo-NiS_(2)/CNFs showed a distinguished durability at 100 m A cm^(-2)at least 100 h.In-situ Raman spectra tracked the evolution and oxidation conversion of S^(2-)to short-chain polysulfides(S_(2)^(2-)–S_(4)^(2-)),ultimately to valueadded S8.Density functional theory calculations unveiled that the introduction of Mo efficiently regulated the d-band center of NiS_(2),reduced the energy barrier in the rate-determining step from S_(2)^(2-)to S32-and the Gibbs free energy of H*adsorption,and thereby significantly promoted SOR and hydrogen evolution reaction(HER).Mo-NiS_(2)/CNFs-based anion exchange membrane water electrolyzer for HER and SOR achieved a current density of 500 m Acm^(-2)at 1.78 V for continuous H_(2)and S8productions.Such a coupling system performed an ultra-low power consumption of 2.127 kW hm^(-3)H_(2)at 500 m A cm^(-2),showing an energysaving hydrogen production and high desulfurization ability for environmental protection and remediation.
