磷化钼基催化剂的制备及其电解水中的应用  

Preparation of Molybdenum Phosphide⁃based Catalyst and Its Application in Water Electrolysis

作　　者：崔博洋 武宏大 余宗宝 耿忠兴 任铁强[1] 史春薇 杨占旭[1] CUI Bo-Yang;WU Hong-Da;YU Zong-Bao;GENG Zong-Xing;REN Tie-Qiang;SHI Chun-Wei;YANG Zhan-Xu(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun 113001,China)

机构地区：[1]辽宁石油化工大学石油化工学院,抚顺113001

出　　处：《应用化学》2022年第3期439-450,共12页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(No.21671092);辽宁省“兴辽英才”创新领军人才项目(No.XLYC1802057);辽宁省-沈阳材料科学国家研究中心联合研发基金(No.2019010280-JH3/301);抚顺英才计划青年拔尖人才(No.FSYC202007001)资助

摘　　要：以十二胺插层的正交三氧化钼为前驱体,次磷酸钠分解产生的PH_(3)作为磷源,在限域的空间内通过原位碳化磷化法,合成了“N掺杂MoP/石墨”复合材料。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、X射线光电子能谱分析(XPS)、拉曼光谱分析(Raman)和比表面积测试法(BET)等手段对700、800和900℃不同磷化温度所得催化剂样品进行微观结构及物理化学性质表征,并考察了其在电解水析氢反应(HER)中的催化性能。结果表明,十二胺分解一部分形成N掺杂的石墨作为导电架构,另一部分分解的氮掺杂磷化钼。800℃磷化样品具有最大的孔径比和电化学活性表面积,其表现出最佳的催化效果(过电势ηonset=111 mV,塔菲尔斜率b=70 mV/dec及27 h的优异稳定性),优于大多数报道的磷化钼催化剂。With dodecyl amine intercalated orthorhombic molybdenum trioxide as the precursor,PH_(3) was produced by decomposition of sodium hypophosphite as the phosphorus source,in a confined space by in-situ carbonization and phosphating method to synthesize“N-doped MoP/graphite”composite materials. The microstructure and physicochemical properties of the catalyst samples obtained at different phosphating temperatures of 700,800 and 900 ℃ were characterized by scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),Raman spectroscopy(Raman),and specific surface area measurement(BET). The catalytic performance in the hydrogen evolution reaction(HER)of water was investigated. The results show that part of dodecyl amine decomposes to form N-doped graphite as the conductive structure,and the other part decomposes to form nitrogen-doped molybdenum phosphide. The 800 ℃ phosphating sample has the largest pore size ratio and electrochemically active surface area, and shows the best catalytic performance(overpotential ηonset=111 mV,Tafel slope b=70 mV/dec and excellent stability of 27 hours)which is better than those of most reported molybdenum phosphide catalysts.

关 键 词：催化剂 电解水 制氢 磷化钼 

分 类 号：O614.6[理学—无机化学]