一种用于肼氧化-复合海水电解制氢的富吡啶氮碳纸
A pyridinic nitrogen-rich carbon paper for hydrazine oxidation-hybrid seawater electrolysis toward efficient H2 generation
马闪闪 1喻博 1夏宝玉 1游波1
作者信息
- 1. Key Laboratory of Material Chemistry for Energy Conversion and Storage(Ministry of Education),Hubei Key Laboratory of Material Chemistry and Service Failure,School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology,Wuhan 430074,China
- 折叠
摘要
丰富的中性海水有望替代高纯淡水用于绿氢制备,然而基于过渡金属材料催化的直接海水电解会因析氯反应(C1ER)引发严重的腐蚀问题并造成二次重金属污染,且析氧反应(OER)的动力学缓慢.本工作中,我们报道了一种稳定的富吡啶氮的碳纸(N-CP-800),可以有效地催化肼氧化反应(HzOR),以取代中性海水中的OER用于节能制氢.结合电化学实验、原位衰减全反射-表面增强傅里叶变换红外光谱表征和密度泛函理论计算,我们发现:相较于吡咯氮和石墨氮,zig和arm构型的吡啶氮更有利于决速步(*H+N2H1)的质子脱附,以促进肼氧化反应.因此,N-CP-800在中性介质中进行HzOR时,仅需0.78 V(相对于可逆氢电势)便可达到10 mA cm-2,低于其OER/C1ER竞争反应.当N-CP-800与非贵金属析氢催化剂CoP耦合进行HzOR-复合海水电解时,仅需1.56 V的电压即可达到10 mA cm-2,并能稳定运行200 h,优于Pt/C和RuO2标准电极对催化的海水电解.
Abstract
Abundant neutral seawater is a potential alter-native to high-purity freshwater for green hydrogen genera-tion,while direct seawater electrolysis catalyzed by transition metals-based materials faces severe corrosion issues due to the chlorine evolution reaction(C1ER)which would pose sec-ondary heavy metal pollution,and sluggish kinetics of oxygen evolution reaction(OER).Herein,we report that the robust metal-free pyridinic nitrogen-rich carbon paper(N-CP-800)can effectively catalyze the hydrazine oxidation reaction(HzOR)to replace OER in neutral simulated seawater for energy-saving hydrogen production.Combined with electro-chemical experiments,operando electrochemical attenuated total reflection surface-enhanced Fourier transform infrared spectroscopy characterizations,and density functional theory calculations reveal that the pyridinic nitrogen with both zig and arm configurations favor the rate-limiting proton deso-rption of the(*H+N2H1)intermediates relative to pyrrolic and graphitic nitrogen for improved HzOR.Consequently,the resulting N-CP-800 enriched with pyridinic nitrogen requires a potential of only 0.78 V vs.reversible hydrogen electrode at 10 mA cm-2 for HzOR in neutral media,lower than those for the competitive OER/C1ER.When coupling N-CP-800 with a nonprecious hydrogen evolution catalyst of CoP,a low voltage of 1.56 V at 10 mA cm-2 is needed to perform the HzOR-as-sisted seawater electrolysis with long-term stability for 200 h,superior to those of Pt/C and RuO2 benchmark in seawater directly.
关键词
seawater electrolysis/hydrazine oxidation/hydrogen evolution/nitrogen doping/metal-free carbonKey words
seawater electrolysis/hydrazine oxidation/hydrogen evolution/nitrogen doping/metal-free carbon引用本文复制引用
基金项目
国家重点研发计划(2021YFA1600800)
Program for Huazhong University of Science and Technology(HUST)Academic Frontier Youth Team()
国家自然科学基金(22075092)
Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)
Analytical and Testing Center of HUST for several physiochemical characterizations()
出版年
2024
NETL
NSTL
万方数据