磷掺杂镍基硫化物超薄纳米片构筑多级微孔双功能催化剂促进高效水电解产氢
Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis
作者单位E-mail
孙强强 商洛学院化学工程与现代材料学院, 陕西省尾矿资源综合利用重点实验室, 陕西省矿产资源清洁高效转化与新材料工程研究中心, 商洛市石墨烯技术与应用研究中心, 商洛 726000  
赵鹏程 商洛学院化学工程与现代材料学院, 陕西省尾矿资源综合利用重点实验室, 陕西省矿产资源清洁高效转化与新材料工程研究中心, 商洛市石墨烯技术与应用研究中心, 商洛 726000  
吴若雨 商洛学院化学工程与现代材料学院, 陕西省尾矿资源综合利用重点实验室, 陕西省矿产资源清洁高效转化与新材料工程研究中心, 商洛市石墨烯技术与应用研究中心, 商洛 726000  
曹宝月 商洛学院化学工程与现代材料学院, 陕西省尾矿资源综合利用重点实验室, 陕西省矿产资源清洁高效转化与新材料工程研究中心, 商洛市石墨烯技术与应用研究中心, 商洛 726000 231052@slxy.edu.cn 
摘要: 利用一步水热合成法在三维多孔泡沫镍(nickel foam,简称NF)表面构筑了由超薄纳米片交织互联形成的多级微孔结构复合材料。当初始混合料液中硫、磷物质的量之比为1∶1时,在120 ℃下水热反应24 h获得了以Ni3S2为主晶相、少量NiPS3为次晶相的镍基复合电催化剂(NiSP/NF)。得益于其超薄纳米片交织形成的独特二级微孔结构,其电化学活性面积较空白NF增加了近14倍,也为其在水电解析氢反应中的应用提供了充足的活性位点和界面通道。同时,受益于晶态Ni3S2和NiPS3所造成的晶格缺陷和强电子作用,材料的本征催化活性也得以显著提升。多方协同作用使得NiSP/NF在全水分解中均表现出优异的催化性能,在1 mol·L-1 KOH溶液中获得10 mA·cm-2的电流密度,需要的析氢和析氧过电位仅为67和212 mV。在全水分解电解槽中,其获得100 mA·cm-2的电流密度所需的槽电压仅为1.878 V,甚至在500 mA·cm-2的高电流密度下需要的分解槽压也仅为2.558 V,优于商业贵金属催化剂,电解水产氢效率显著提高。NiSP/NF在全水分解中还呈现了极优异的长效稳定性及耐用性,在电流密度为500 mA·cm-2时经过120 h的恒电流催化后,其增加的分解槽压不足0.03 V。
关键词: 磷掺杂  析氢反应  析氧反应  协同催化
基金项目: 陕西省青年创新团队科学研究计划项目(No.23JP039)、陕西高校青年创新团队(No.20JCS062)、陕西省科技厅项目(No. 2022JM066)、商洛市科技发展计划项目(No.2023-G-0007)、商洛学院科研发展平台专项(No.22KYZX01)和大学生创新创业训练计划项目(No.S202111396034,S202211396016)资助。
Abstract: The multistage microporous electrocatalysts to assist the energy-efficient hydrogen generation from water electrolysis were fabricated on the surface of three-dimensional porous foam (NF) by a one-step hydrothermal synthesis strategy. When the molar ratio of sulfur to phosphorus in the initial mixed solution was 1∶1, an amorphous P-doped nickel-based sulfide (NiSP/NF) electrocatalyst, with Ni3S2 and NiPS3 as the main and secondary crystalline phase, respectively, was obtained by hydrothermal treatment at 120 ℃ for 24 h. Thanks to its unique bi-hierarchy microporous structure composed of interwoven interconnected ultra-thin nanosheets, yielding the nearly 14-fold increased electrochemical active surface area (ECSA), sufficient active sites and interface channels are provided for hydrogen evolution reaction (HER) during water splitting. Meanwhile, benefiting from the lattice defects created by crystalline Ni3S2 and the strong electronic interactions with crystalline P doping phases, respectively, the intrinsically catalytic activity of nickel-based electrocatalyst was significantly enhanced. The synergistic effects enable NiSP/NF to exhibit remarkable performances during the whole water splitting, achieving a current density of 10 mA·cm-2 in 1 mol·L-1 KOH solution with overpotentials for HER and OER as low as 67 and 212 mV, respectively. Assembled as an electrolyzer for overall water splitting (OWS), a current density of 100 mA·cm-2 can be achieved only needing a cell voltage of 1.878 V, even at 500 mA·cm-2 the needed cell voltage was only 2.558 V for NiSP/NF, which is dramatically superior to noble metal catalysts and helpful to improve hydrogen production efficiency for water electrolysis. Particularly, as a bifunctional electrocatalyst, NiSP/NF also exhibited excellent long-term stability and durability, because of less than a 0.03 V cell voltage increase after running a 120-hour chronopotentiometric test at 500 mA·cm-2.
Keywords: P-doping  hydrogen evolution reaction  oxygen evolution reaction  synergistic catalysis
投稿时间:2023-12-02 修订日期:2024-03-27
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孙强强,赵鹏程,吴若雨,曹宝月.磷掺杂镍基硫化物超薄纳米片构筑多级微孔双功能催化剂促进高效水电解产氢[J].无机化学学报,2024,40(6):1151-1161.
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