【作者】 孟晓；

【导师】 程合锋； 黄柏标；

【作者基本信息】 山东大学 ， 材料学， 2023， 硕士

【摘要】 当前人类社会面临严重的能源危机和环境污染问题,因此寻求一种绿色清洁的能源来取代传统的化石燃料具有重要意义。氢能由于具有燃烧值高、可存储等优点,引起了研究人员的广泛关注。传统的制氢方式会引起环境污染,相比之下,利用太阳能驱动的水分解产氢是绿色、无污染、可持续的手段,具有更潜在的应用前景。太阳能驱动的水分解反应在近几十年来取得了重要进展,然而仍受太阳能到氢能转换效率低、稳定性差及贵金属催化剂成本高等问题的限制,这也是制约其大规模实际应用和发展的重要瓶颈。因此,实现高效、稳定且成本低廉的太阳能驱动水分解反应具有重要的科学研究和实际应用价值。相比起价格高昂的贵金属,镍基材料储量丰富、成本低,同时具有易于调控的电子结构、高导电性以及良好的耐腐蚀性等优点,在电催化水分解领域有着广阔的应用前景。通过对镍基材料进行探索研究,有望开发出性能优异且成本低廉的水分解电催化剂。基于此,我们以镍基材料作为研究对象,根据电子结构-催化性能间的构效关系,开发了性能优越的析氢反应(HER)和析氧反应(OER)催化剂,进一步耦合III-V族光伏半导体材料,设计了太阳能驱动的光化学转换器件,实现了高效、稳定且成本较低的太阳能驱动水分解反应。本论文的主要研究内容如下:第一章中,我们首先阐述了太阳能驱动的水分解反应概况,接着介绍了电催化水分解反应的机理以及镍基水分解电催化剂的研究进展,最后针对目前研究存在的问题介绍了本论文的选题意义和研究内容。在第二章中,针对当前太阳能驱动的水分解反应稳定性差的问题,我们从镍基水分解电催化剂的构效关系出发,通过高温还原法制备了纳米线阵列的MoNi4/MoO2双功能电催化剂。MoNi4/MoO2具有较高的电化学活性面积、电导率、高效的电催化析氢析氧半反应活性和稳定性,因此,MoNi4/MoO2双功能催化剂展现出优异的电催化水分解性能和长时间稳定性。通过与三结III-V族光伏半导体进行空间耦合,搭建了太阳能驱动的水分解反应系统,实现了高效、稳定的太阳能驱动水分解反应性能。最后进一步搭建了无导线联接的集成人工树叶系统,获得了高效稳定的太阳能驱动水分解反应性能。第三章中,针对当前太阳能驱动的水分解效率低的问题,我们从提高水分解反应中动力学缓慢的析氧反应过程出发,提高NiFe基层状双氢氧化合物(NiFe-LDHs)活性位点数量和稳定性。通过对水热合成的NiFe-LDHs进行退火处理,提高了电催化OER的活性和稳定性。通过与第二章中的MoNi4/MoO2析氢反应催化剂组合,制备了高效的MoNi4/MoO2||NiFe-LDHs电化学水分解全电池。进一步耦合三结光伏半导体,搭建了太阳能驱动的水分解反应系统,实现了高效长时间稳定的水分解反应性能。在第四章中,我们对论文进行了整体总结。介绍了本论文的研究内容、主要创新点以及存在的问题,同时提出了相应的解决方案,并对接下来的工作进行了展望。更多还原

【Abstract】 Currently,human society is facing serious energy crises and environmental pollution problems,so it is important to seek a green and clean energy source to replace traditional fossil fuels.Hydrogen energy has attracted a lot of attention from researchers because of its advantages such as high combustion value and storage.Traditional hydrogen production methods cause environmental pollution.In contrast,the use of solar-driven photocatalytic water splitting for hydrogen production is a green,non-polluting,and sustainable means with more potential application prospects.The development of solar-driven overall water splitting reaction has made important progress in recent decades,however,it is still limited by the low efficiency of solar-to-hydrogen conversion,poor stability,and high cost of precious metal catalysts,which is an important bottleneck limiting its large-scale practical application and development.Therefore,the realization of efficient,stable,and low-cost solar-driven hydrolysis reactions is of great scientific research and practical application value.Compared with expensive precious metals,nickel-based materials have the advantages of abundant reserves,low-cost,easily tunable electronic structure,high electrical conductivity,and good corrosion resistance,which have broad application prospects in the field of electrocatalytic water splitting.By exploring nickel-based materials,it is expected to develop electrocatalysts for water splitting with excellent performance and low cost.Based on this,we have developed superior performance hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)electrocatalyst based on the conformational relationship between electronic structure and catalytic performance using nickel-based materials,further coupled with III-V photovoltaic semiconductor materials,and designed solar-driven photochemical conversion devices to achieve efficient,stable and low-cost solar-driven hydrolysis reaction performance.The main research of this thesis is as follows:In chapter 1,we first describe the overview of the solar-driven hydrolysis reaction,then introduce the mechanism of electrocatalytic overall water splitting reaction and the research progress of nickel-based water splitting electrocatalyst,and finally introduce the significance of the topic and the research content of this thesis because of the current research problems.In Chapter 2,to address the current problem of poor stability of solar-driven hydrolysis,we prepared MoNi4/MoO2 bifunctional electrocatalysts with nanowire arrays by hightemperature reduction method from the conformational relationship of nickel-based water splitting electrocatalysts.MoNi4/MoO2 has a high electrochemical active area,efficient electrocatalytic hydrogen evolution and oxygen evolution half reaction active and stability,thus the MoNi4/MoO2 bifunctional catalyst exhibited excellent electrocatalytic hydrolysis performance and long-term stability.By spatially coupling with triple-junction III-V photovoltaic semiconductors,a solar-driven water splitting reaction system was built to achieve an efficient and stable solar-driven hydrolysis reaction performance.Finally,the integrated artificial leaf system without wire coupling was further constructed to achieve an efficient and stable solar-driven water splitting reaction.In Chapter 3,to address the current problem of low efficiency of solar-driven water splitting,we improve the stability and the number of active sites of NiFe base double hydroxides(NiFe-LDHs)by improving the kinetically slow oxygen evolution reaction process in water splitting reactions.The activity and stability of the electrocatalytic OER were improved by annealing the hydrothermally synthesized NiFe-LDHs.By combining with the HER electrocatalyst MoNi4/MoO2 in Chapter 2,highly efficient MoNi4/MoO2‖NiFe-LDHs electrochemical water splitting full cells were prepared.Further coupled with a triple-junction photovoltaic semiconductor,a solar-driven water splitting reaction system was built to achieve efficient and stable hydrolysis reaction performance for a long time.In Chapter 4,we present an overall summary of the thesis.The research content,main innovation points,and problems of this thesis are introduced,and corresponding solutions are also proposed,and the next work has prospected.更多还原