Co-Cu双金属MOF纳米片的合成及电催化析氧反应研究  

Synthesis of Co-Cu bimetallic MOF nanosheets and their application in electrocatalytic oxygen evolution reaction

作　　者：龚盛鹏 刘杨[1,2] 秦勇[1] Gong Shengpeng;Liu Yang;Qin Yong(School of Petrochemical Engineering,Changzhou University,Changzhou 213164;School of Biomedical Engineering,Changzhou University,Changzhou 213164)

机构地区：[1]常州大学石油化工学院,常州213164 [2]常州大学生物医药工程学院,常州213164

出　　处：《化工新型材料》2024年第1期247-252,共6页New Chemical Materials

基　　金：国家自然科学基金(81900814);浙江省重点研发计划项目(2020C03003)。

摘　　要：析氧反应(OER)是电解水制氢的阳极反应,其反应速度仅为阴极析氢反应(HER)速度的十分之一。为了加快反应速度,通常需要使用RuO_(2)等贵金属催化剂,但贵金属的稀缺性及较低的催化活性限制了其发展。金属有机框架(MOFs)材料是一类非常具有发展前景的OER电催化剂,然而目前MOFs在电催化OER中的应用也面临诸多问题,例如制备过程复杂、配体价格昂贵、催化活性低等。在此,提出了一种简易的表面活性剂辅助法制备Co-Cu双金属MOF纳米片的方法,在室温下搅拌对苯二甲酸和硝酸铜、硝酸钴,十二烷基硫酸钠的混合溶液,即可得到尺寸约为100~200nm的Co-Cu MOF纳米片。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)等手段对材料结构进行了表征。电催化OER性能测试表明,Co-Cu MOF(n_(Co)∶n_(Cu)=2∶1)在碱性条件下对OER反应具有优异的OER活性,达到电流密度10mA/cm^(2)时的过电位(η_(10))仅为320mV,明显优于单一的Co MOF(430mV)和Cu MOF(几乎没有活性)。理论研究表明,Cu^(2+)的加入能提高Co MOF中Co的氧化态,进而提高其OER活性。该法操作简单、原料价格便宜,适合大规模生产,具有较好的应用前景。Oxygen evolution reaction(OER) is an anode reaction of electrocatalytic water-splitting hydrogen production,and its reaction rate is only one tenth that of the corresponding cathode hydrogen evolution reaction(HER).In this context,noble metal catalysts such as RuO_(2) are usually utilized to accelerate the rate.Unfortunately,the scarcity of noble metals and low catalytic activity restrict their development.Metal organic framework(MOFs) materials have been proved a kind of promising electrocatalysts for OER.Up to date,the application of MOFs in OER still face some problem,such as the complicated fabricating process,expensive ligands,and low catalytic activity.Herein,a simple surfactant-assisted method was proposed to prepare Co-Cu bimetallic MOF nanosheets.By stirring the mixed solution of terephthalic acid,copper nitrate,cobalt nitrate and sodium dodecyl sulfate at room temperature,Co-Cu MOF nanosheets with a size of about 100~200nm could be obtained.The structure of the material was characterized by XRD,XPS,SEM and TEM.The electrocatalytic OER performance was tested.The results showed that Co-Cu MOF(n_(Co)∶n_(Cu)=2∶1) had excellent OER activity under alkaline conditions,and only 320 mV overpotential(η_(10)) was needed to achieve the current density of 10 mA/cm^(2),significantly better than that of the individual Co MOF(η_(10)=430mV) and Cu MOF(almost no activity).The further theoretical study showed that the addition of Cu^(2+) improved the oxidation state of Co in Co MOF,thus enhancing its OER activity.The method proposed here was simple,and the raw material needed was very cheap,which was suitable for large-scale production.The as-obtained Co-Cu MOF nanosheets had a good application prospect.

关 键 词：电催化 金属有机框架 析氧反应 

分 类 号：O646[理学—物理化学]