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
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
电化学分解水制氢是实现可持续、绿色制氢的重要途径,但由于阳极析氧反应(OER)缓慢的反应速率严重阻碍了全水解的效率。为从根本上解决此问题,利用低理论电位的硫离子氧化反应(SOR)取代OER,能极大的降低水电解的电压,提升水解效率,同时...电化学分解水制氢是实现可持续、绿色制氢的重要途径,但由于阳极析氧反应(OER)缓慢的反应速率严重阻碍了全水解的效率。为从根本上解决此问题,利用低理论电位的硫离子氧化反应(SOR)取代OER,能极大的降低水电解的电压,提升水解效率,同时在阳极获得增值产物。本工作通过共沉淀法成功制备出六氰钴酸钴(CoHCC)材料,并将CoHCC负载到泡沫镍(NF)基底上制备工作电极(CoHCC/NF),作为高效的硫离子氧化反应催化剂。在三电极体系下测试其SOR催化性能,CoHCC/NF仅需要0.31 V vs.RHE的低电压就能达到100 mA·cm^(-2)的电流密度,这远优于Co(OH)_(2)/NF和NF。此外,CoHCC/NF有最低的Tafel斜率(77mA·dec^(-1))和最小的电化学阻抗,且表现出良好的稳定性。同时,在两电极体系下模拟实际电解水制氢,测试表明新型耦合反应系统(SOR-HER)在达到100 mA·cm^(-2)电流密度时所需的电压远低于传统的全水解(OER-HER)制氢系统,本工作为超低能耗制氢和硫回收提供了一条有吸引力的途径。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
电解水是可持续绿色制氢的重要方法,但阳极缓慢的析氧反应(OER)严重阻碍电解水能量转化效率的提升,利用氧化电位较低的硫离子氧化反应(SOR)替代OER与阴极析氢反应耦合可以实现能耗的大幅降低。本文通过共沉淀法成功制备了一种钴基沸石...电解水是可持续绿色制氢的重要方法,但阳极缓慢的析氧反应(OER)严重阻碍电解水能量转化效率的提升,利用氧化电位较低的硫离子氧化反应(SOR)替代OER与阴极析氢反应耦合可以实现能耗的大幅降低。本文通过共沉淀法成功制备了一种钴基沸石咪唑酯骨架材料(ZIF-67),通过XRD、SEM、XPS测试手段对催化材料进行了物相分析,结果表明制备的ZIF-67催化材料由许多堆积在一起的立方体纳米颗粒组成。在三电极体系中对其进行SOR催化性能测试,将ZIF-67涂敷在泡沫镍基底上作为工作电极(ZIF-67/NF),ZIF-67/NF仅需0.361 V vs.RHE的电压就可以达到50 mA·cm^(-2)的电流密度,其电催化活性远优于Co(OH)2/NF和NF。ZIF-67/NF还表现出最低的Tafel斜率(73 mA·dec^(-1))和最小的电化学阻抗,并展现出良好的稳定性。此外,对基于SOR的两电极耦合制氢体系的电化学性能进行了测试,发现所需施加电压远小于传统的全水解制氢系统,为超低能耗制氢提供一种切实可行的方案。展开更多
本文通过微波法超快速制备了泡沫镍(NF)负载的Co/Zn复合氧化物(Co-Zn/NF)。XRD测试表明生成的Co/Zn复合氧化物具有低结晶度。采用线性扫描伏安法(LSV)测试了Co-Zn/NF在碱性条件下的电催化硫离子氧化性能。与泡沫镍负载的单金属氧化物(Co...本文通过微波法超快速制备了泡沫镍(NF)负载的Co/Zn复合氧化物(Co-Zn/NF)。XRD测试表明生成的Co/Zn复合氧化物具有低结晶度。采用线性扫描伏安法(LSV)测试了Co-Zn/NF在碱性条件下的电催化硫离子氧化性能。与泡沫镍负载的单金属氧化物(Co/NF和Zn/NF)相比,Co-Zn/NF表现出更好的催化性能。在含有1 mol·L^(-1)Na2S和1 mol·L^(-1)NaOH的电解液中,Co-Zn/NF达到100 m A·cm^(-2)的电流密度所需的电位仅为0.28 V vs RHE,并且在恒定100 m A·cm^(-2)的电流密度下,长时间工作35小时后仍保持高的催化性能。此外,组装非对称电解槽(阳极:硫离子氧化反应(sulfion oxidation reaction,SOR)用1 mol·L^(-1)Na2S和1mol·L^(-1)NaOH为电解质,阴极:析氢反应(hydrogen evolution reaction,HER)用1 mol·L^(-1)Na OH为电解质)进行双电极硫氧化辅助电解水制氢测试,与传统的碱性电解水相比,达到100 m A·cm^(-2)电流密度所需的能耗降低了46%。本工作为低能耗电化学制氢提供了一种新思路,并证明了SOR耦合HER电解水制氢具有实际应用的可行性。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 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.
文摘电化学分解水制氢是实现可持续、绿色制氢的重要途径,但由于阳极析氧反应(OER)缓慢的反应速率严重阻碍了全水解的效率。为从根本上解决此问题,利用低理论电位的硫离子氧化反应(SOR)取代OER,能极大的降低水电解的电压,提升水解效率,同时在阳极获得增值产物。本工作通过共沉淀法成功制备出六氰钴酸钴(CoHCC)材料,并将CoHCC负载到泡沫镍(NF)基底上制备工作电极(CoHCC/NF),作为高效的硫离子氧化反应催化剂。在三电极体系下测试其SOR催化性能,CoHCC/NF仅需要0.31 V vs.RHE的低电压就能达到100 mA·cm^(-2)的电流密度,这远优于Co(OH)_(2)/NF和NF。此外,CoHCC/NF有最低的Tafel斜率(77mA·dec^(-1))和最小的电化学阻抗,且表现出良好的稳定性。同时,在两电极体系下模拟实际电解水制氢,测试表明新型耦合反应系统(SOR-HER)在达到100 mA·cm^(-2)电流密度时所需的电压远低于传统的全水解(OER-HER)制氢系统,本工作为超低能耗制氢和硫回收提供了一条有吸引力的途径。
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.
文摘电解水是可持续绿色制氢的重要方法,但阳极缓慢的析氧反应(OER)严重阻碍电解水能量转化效率的提升,利用氧化电位较低的硫离子氧化反应(SOR)替代OER与阴极析氢反应耦合可以实现能耗的大幅降低。本文通过共沉淀法成功制备了一种钴基沸石咪唑酯骨架材料(ZIF-67),通过XRD、SEM、XPS测试手段对催化材料进行了物相分析,结果表明制备的ZIF-67催化材料由许多堆积在一起的立方体纳米颗粒组成。在三电极体系中对其进行SOR催化性能测试,将ZIF-67涂敷在泡沫镍基底上作为工作电极(ZIF-67/NF),ZIF-67/NF仅需0.361 V vs.RHE的电压就可以达到50 mA·cm^(-2)的电流密度,其电催化活性远优于Co(OH)2/NF和NF。ZIF-67/NF还表现出最低的Tafel斜率(73 mA·dec^(-1))和最小的电化学阻抗,并展现出良好的稳定性。此外,对基于SOR的两电极耦合制氢体系的电化学性能进行了测试,发现所需施加电压远小于传统的全水解制氢系统,为超低能耗制氢提供一种切实可行的方案。
文摘本文通过微波法超快速制备了泡沫镍(NF)负载的Co/Zn复合氧化物(Co-Zn/NF)。XRD测试表明生成的Co/Zn复合氧化物具有低结晶度。采用线性扫描伏安法(LSV)测试了Co-Zn/NF在碱性条件下的电催化硫离子氧化性能。与泡沫镍负载的单金属氧化物(Co/NF和Zn/NF)相比,Co-Zn/NF表现出更好的催化性能。在含有1 mol·L^(-1)Na2S和1 mol·L^(-1)NaOH的电解液中,Co-Zn/NF达到100 m A·cm^(-2)的电流密度所需的电位仅为0.28 V vs RHE,并且在恒定100 m A·cm^(-2)的电流密度下,长时间工作35小时后仍保持高的催化性能。此外,组装非对称电解槽(阳极:硫离子氧化反应(sulfion oxidation reaction,SOR)用1 mol·L^(-1)Na2S和1mol·L^(-1)NaOH为电解质,阴极:析氢反应(hydrogen evolution reaction,HER)用1 mol·L^(-1)Na OH为电解质)进行双电极硫氧化辅助电解水制氢测试,与传统的碱性电解水相比,达到100 m A·cm^(-2)电流密度所需的能耗降低了46%。本工作为低能耗电化学制氢提供了一种新思路,并证明了SOR耦合HER电解水制氢具有实际应用的可行性。
