微波法快速、原位合成NiFe LDH纳米片阵列用于高效电催化水氧化  

Rapid and in-situ synthesis of NiFe LDH nanosheet array using microwave method for efficient electrocatalytic water oxidation

作　　者：王沙沙 陆徐云 常亚楠 李晓萱 刘影 包建春[1] Shasha Wang;Xuyun Lu;Yanan Chang;Xiaoxuan Li;Ying Liu;Jianchun Bao(School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China)

机构地区：[1]南京师范大学化学与材料科学学院,南京210023

出　　处：《科学通报》2025年第2期193-204,共12页Chinese Science Bulletin

基　　金：国家自然科学基金(22102073,22075147)资助。

摘　　要：氧气析出反应(oxygen evolution reaction,OER)复杂的动力学和高能量势垒严重制约了电解水生产氢能的效率.基于此,本工作报道了一种简单、高效的微波合成策略,可以在碳布表面快速、原位生长层状双金属氢氧化物阵列(layered double hydroxide/carbon cloth,LDH/CC),用以提升OER性能.研究发现,溶剂类型对LDHs的原位生长起着至关重要的作用.相比于纯水、乙二醇水溶液和季戊四醇水溶液溶剂,丙三醇水溶液具有适宜的极性,可以有效调控金属离子的表面能和反应过程中金属离子的成核/迁移,进而促进LDHs在碳布表面的原位、均匀生长.与传统的水热法和电沉积法相比,微波法合成的NiFe LDH/CC具有氧缺陷含量高、电化学活性位点丰富、界面电荷转移电阻低和内在活性高等优点.以OER为探针反应,探究并比较了以不同溶剂及合成方法制得的NiFe LDH/CC的电催化性能.测试表明,以丙三醇水溶液为溶剂、采用微波法合成的NiFe LDH/CC性能最好,在100 mA cm^(-2)的过电位(overpotential,η)仅为257 mV(η_(100)),400 mA cm^(-2)的过电位仅为331 mV(η_(400)),持续测试100 h后性能仍保持95%,显著优于以乙二醇水溶液(287和386 mV)、季戊四醇水溶液(309和406 mV)为溶剂的对比样,以及水热法(279和434 mV)、电沉积法(293和380 mV)合成NiFe LDH/CC的电催化性能.进一步,这些性能优于近些年报道的很多过渡金属化合物.这种微波合成策略不仅适用于NiFe LDH,还可以原位合成NiMn LDH、CoFe LDH、NiCo LDH,为高活性LDH的原位、快速合成提供了一种新方法.The complex kinetics and high energy barrier of oxygen evolution reaction(OER)seriously restrict the efficiency of hydrogen production in overall water splitting.Layered double hydroxides(LDHs)have reasonable electrocatalytic OER ability,but the resulting performance is unsatisfactory;moreover,their rapid,large-scale,and in situ synthesis remains a great challenge.Compared to the traditional hydrothermal,electrodeposition and co-precipitation methods,microwave synthesis methods have the advantages of cleanliness,high efficiency,and low energy consumption.Importantly,microwave methods can generate many defects to improve the electrocatalytic performance.The microwave-assisted synthesis of LDHs has been reported,but it was limited to powdered nano/micromaterials.The use of microwave methods to grow nano/microarrays in situ on a substrate surface has not been reported.Compared with powders,arrays have multiple advantages,such as favorable electrolyte diffusion,proton/electron transport,and direct use for electrochemical testing without the need for additional binders,so there is an urgent need to develop strategies for the in-situ synthesis of nano/microarrays using microwave methods.Based on these studies,this paper reports a simple and effective microwave synthesis strategy for growing layered double hydroxides arrays in situ on the surface of a carbon cloth(CC),termed as LDH/CC to improve the OER performance.The type of solvent plays a crucial role in the in situ growth of LDHs.Compared to pure water,ethylene glycol,and pentaerythritol aqueous solvents,glycerol has a suitable polarity that can effectively regulate the surface energy of metal ions and the nucleation/migration of metal ions during the synthesis process,promoting the in situ and uniform growth of LDHs on the CC surface.When applied to the electrocatalytic OER,the NiFe LDH/CC catalyst synthesized using glycerol as a solvent exhibited excellent electrocatalytic performance,with a low overpotential of 257 mV(η_(100)),279 mV(η_(200)),and 331 mV(η_(40

关 键 词：电催化 氧气析出反应 微波法 NiFe层状双金属氢氧化物 

分 类 号：TQ116.2[化学工程—无机化工] O643.36[理学—物理化学]