金属性Ni_(3)N纳米粒子的制备与乙二醇电氧化性能  

Preparation of Metallic Ni_(3)N Nanoparticles and Its Electrooxidation Performance for Ethylene Glycol

作　　者：杨镇鸿 干晓娟 王书哲 段君元 翟天佑[1] 刘友文 Yang Zhenhong;Gan Xiaojuan;Wang Shuzhe;Duan Junyuan;Zhai Tianyou;Liu Youwen(State Key Laboratory of Material Processing and Die&Mould Technology,School of Materials Science and Engineering,Huazhong University of Science and Technology,Wuhan 430074)

机构地区：[1]华中科技大学材料科学与工程学院材料成形与模具技术全国重点实验室,武汉430074

出　　处：《化学学报》2023年第11期1471-1477,共7页Acta Chimica Sinica

基　　金：大学生创新创业训练计划(No.S202210487007);国家自然科学基金(No.22071069)资助。

摘　　要：利用小分子电催化氧化反应耦合水解制氢不仅有助于降低阳极反应过电位,提高析氢反应(HER)效率,而且产生高附加值的化学品,是提升电催化水分解性能的有效策略.其关键是开发具有高导电性和低氧化电位的非贵金属电催化剂.以Ni(OH)_(2)纳米片为前驱物,通过退火氮化工艺,制备了具有低氧化电位和高导电性的金属相Ni_(3)N纳米颗粒(Ni_(3)N-NPs).与Ni(OH)_(2)相比,Ni_(3)N-NPs具有较小的法拉第电阻,更低的氧化电位(1.36 V时达到10 mA·cm^(-2)),较小的Tafel斜率(29 mV·dec^(-1)),表现出更好的乙二醇(EG)电催化氧化性能.在1.36 V时,Ni_(3)N-NPs电催化氧化EG生成甲酸盐的法拉第效率高达91.16%.通过X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)对反应前后Ni_(3)N-NPs结构进行详细表征发现,在电催化EG氧化过程中,Ni_(3)N-NPs表面被氧化生成NiOOH,同时EG在催化剂表面发生脱H氧化生成甲酸,H同步还原Ni OOH并将其转化为Ni(OH)_(2).此外,Ni_(3)N-NPs对有机小分子电催化氧化具有良好的普适性.Coupled small molecule electrocatalytic oxidation reaction can not only reduce anode overpotential,improve hydrogen evolution reaction(HER)efficiency,but also produce high value-added chemicals,which is an effective strategy to improve the performance of electrocatalytic water splitting.The development of non-noble metal based electrocatalysts with high conductivity and low oxidation potential is the key issue.Herein,Ni_(3)N nanoparticles(Ni_(3)N-NPs)with low oxidation potential and high conductivity were prepared by annealing and nitriding Ni(OH)_(2) nanosheets precursors.Compared with Ni(OH)_(2),Ni_(3)N-NPs has a smaller Faraday resistance,a lower oxidation potential,a smaller Tafel slope(29 mV•dec^(-1)),and exhibits the better electrocatalytic oxidation performance towards ethylene glycol(EG).At 1.36 V,the Faraday efficiency of electrocatalytic EG oxidation to formate reached 91.16%.The structure of Ni_(3)N-NPs before and after the electrocatalytic oxidation reaction was characterized in detail by X-ray diffractometer(XRD),transmission electron microscope(TEM)and X-ray photoelectron spectroscopy(XPS).It was found that in the electrocatalytic EG oxidation process,the surface of Ni_(3)N-NPs was oxidized into NiOOH,while EG underwent dehydrogenation and oxidation to form formic acid on the catalyst surface,and the NiOOH was synchronously reduced by H and converted into Ni(OH)_(2).In addition,Ni_(3)N-NPs has good uni-versality for electrocatalytic oxidation of small organic molecules.

关 键 词：电催化 电解水 乙二醇 Ni(OH)_(2) Ni_(3)N 

分 类 号：O643.36[理学—物理化学] TB383.1[理学—化学]