MoSe_(2)纳米片耦合Pt纳米颗粒用于高效双功能催化甲醇辅助水电解制氢  

Efficient bi‐functional catalysis of coupled MoSe_(2) nanosheet/Pt nanoparticles for methanol‐assisted water splitting

作　　者：乔蔚 于立策 常进法 杨甫林 冯立纲[1] Wei Qiao;Lice Yu;Jinfa Chang;Fulin Yang;Ligang Feng(School of Chemistry and Chemical Engineering,Yangzhou University,Yangzhou 225002,Jiangsu,China;NanoScience Technology Center,University of Central Florida,FL 32826,Orlando,USA)

机构地区：[1]扬州大学化学化工学院,江苏扬州22500 [2]中佛罗里达大学纳米科学技术中心,奥兰多,美国

出　　处：《Chinese Journal of Catalysis》2023年第8期113-123,共11页催化学报（英文）

基　　金：国家自然科学基金(21972124,22102105,22272148).

摘　　要：化石燃料的大量消耗所带来的全球性挑战推动人们大力发展清洁和可持续的能源.氢能作为一种绿色、无污染的能源载体,是能源向绿色经济转换的关键,而利用可再生能源进行的电解水制氢被认为是实现绿色制氢的最佳选择.然而由于析氧反应(OER)的氧化电位(1.23 V)较高,动力学缓慢,实际水电解需要更多的能量输入.具有低氧化电位的甲醇辅助水电解(0.016 V)可以匹配可再生能源实现低能耗电解制氢,受到了广泛关注.开发高效的用于催化甲醇氧化(MOR)和析氢反应(HER)的双功能催化剂是实现这一愿景的前提.传统的Pt基催化剂容易受到阳极侧MOR过程中产生的CO中间体毒化,严重影响甲醇辅助水电解制氢的效率.为了提升Pt基催化剂的催化活性和稳定性,一种有效的策略是引入合适的功能组分来促进催化反应.例如,贵金属颗粒和亲氧化成分(如过渡金属氧化物和磷化物)之间的金属-载体相互作用可以有效提高Pt基催化剂的抗CO中毒能力.过渡金属硒化物由于其优良的金属性和亲氧性作为催化促进剂受到越来越多的关注.硒化钼(MoSe_(2))具有良好的稳定性和导电性并且其2H相中的不饱和边缘具有水活化和解离活性,同时其吸附H原子的吉布斯自由能(ΔGH^(*))接近于零.考虑到MoSe_(2)的高水活化/解离能力,本文成功制备了二维MoSe_(2)纳米片负载的Pt纳米粒子复合催化剂(Pt/MoSe_(2))用于高效甲醇电解制氢.密度泛函理论计算表明,亲氧组分MoSe_(2)显著优化了CO^(*)和H^(*)在Pt表面的吸附能,从而大大提高了甲醇辅助水电解的活性和稳定性.其中,Pt/MoSe_(2)的甲醇氧化峰值电流密度为67.8 m Acm^(-2),是商业Pt/C催化剂的2.5倍;在10 m A·cm^(-2)的电流密度下,HER的过电位低至32 m V.由Pt/MoSe_(2)|Pt/MoSe_(2)组装的两电极电解槽驱动10 m A·cm^(-2)的电流密度仅需要0.67 V的电压,与相同条件下的水电解相比节省了约1.Efficient metal-support interaction induced high catalysis performance plays a significant role in energy conversion reactions.Herein,two-dimensional(2D)MoSe2 nanosheet-coupled Pt nanoparticles as efficient bi-functional catalysts were demonstrated for hydrogen production from the methanol-assisted water-splitting reaction.The oxophilic MoSe_(2) component with 2D structures optimized the adsorption of CO^(*)and H^(*)on Pt sites as demonstrated by spectroscopic and theoretical analysis,which resulted in enhanced catalytic ability in methanol-assisted water splitting reaction.The peak current density was 2.5 times higher than that of commercial Pt/C catalyst for methanol oxidation and a small overpotential of 32 mV was demanded to achieve a current density of 10 mA cm^(–2) for hydrogen evolution reaction in the methanol-containing electrolyte.When serviced as both cathode and anode,a low cell voltage of 0.66 V was required at 10 mA cm^(–2),significantly lower than that of 1.75 V required for water splitting.The high performance can be attributed to the oxophilicity of MoSe_(2) and their strong metal-support interaction that promoted the charge transfer and anti-CO poisoning of Pt sites.This work would be instructive for the development of novel bi-functional catalyst platforms for methanol-assisted water splitting in hydrogen production.

关 键 词：硒化钼 二维结构 制氢 甲醇辅助水分解 Pt纳米颗粒 

分 类 号：O64[理学—物理化学]