过渡金属化合物催化剂在电解水析氢中的应用进展

概述了过渡金属氧化物、硫化物、磷化物以及其复合材料作为电解水析氢反应催化剂的应用进展。讨论了过渡金属化合物中纳米结构、杂原子掺杂和缺陷工程等不同改性方法对电解水析氢反应的影响,分析了过渡金属化合物复合材料在电解水析氢反应中具有高效率的原因。总结了过渡金属化合物催化剂在电解水析氢领域应用面临的挑战和未来的机遇。     

电催化析氢反应催化材料的研究进展

氢能源作为21世纪的理想新能源,备受社会各界的关注。制取氢气的方法主要有3个大方向:化石能源制备氢气、生物能制备氢气、电解水制备氢气。电解水产生氢气更高效、安全和低成本,且电解水制氢是最环保、产物纯度最高的制备方式。目前,贵金属铂是电催化析氢反应中催化性能最好的催化材料,但昂贵的价格及在自然界中的低储量限制了其大规模的应用。近年来,人们对析氢催化材料进行了大量的研究与优化,以期开发出高效且低价的析氢反应(HER)中的催化材料。本文综述了HER中的析氢催化材料的研究进展,并对其未来的发展进行了展望。     

中空碳基材料在电解水中的研究进展

氢能所具有的清洁、高能量密度特点,使其成为一种未来的理想能源。相较于石油、天然气等的热解制氢技术,利用可再生清洁能源进行电催化分解水制氢具有高效和清洁无污染的特点,且获得氢气产物纯度高,具备大规模发展的潜力。而在大规模水电解过程中,电催化剂是不可或缺的元素之一。它能有效地加速电解水在阴阳两极反应的动力学过程。传统的贵金属基催化剂具有良好的电催化析氢、析氧活性,但成本高昂、储量稀缺,从而限制了其规模化地推广及应用。开发新型高效廉价的非贵金属基电催化剂已成为时下研究热点。中空碳基纳米材料集成了中空材料和碳基材料的优势,作为电催化剂,在电解水方面有着潜在的应用价值。本文总结了近年来微纳米结构碳基中空材料作为新型电解水催化剂的研究进展,介绍了高效碳基中空析氧/析氢催化剂的设计原则和相应的设计策略,并对开发持久高效的中空碳基电解水催化剂进行了总结和展望。     

金属磷化物电催化产氢的研究进展

氢气被认为是能替代传统化石燃料的一种新型能源,因此众多研究者试图寻找一种绿色方便的制氢技术,其中电解水产氢受到广泛关注,而电解水使用的催化剂是一些贵金属催化剂(Pt、Pd等),这就极大的增加电解水技术的成本,因此需要开发一种非贵金属催化剂。最近,过渡金属磷化物被认为是高活性、耐久性、高稳定性可替代贵金属的高性能催化剂,本文主要总结了金属磷化物作为电催化剂在电解水中的研究进展、趋势和挑战。     

电催化水分解制氢阳极关键材料的研究进展

电催化水分解制氢是目前实现大规模制氢的有效手段,但是阳极电催化析氧反应因其较高的反应能垒导致电催化制氢过程中大量的能源被消耗,严重阻碍了其工业化应用,所以开发高效的析氧电催化剂对制氢工业的推进有着重要的意义。对近年来过渡金属磷化物、硫化物以及硒化物在电催化析氧反应中的研究进行了综述,最后对非贵金属析氧电催化剂的研究趋势进行了展望。     

过渡金属基电催化析氢材料的研究进展

氢能是一种无污染的可持续新能源,因此具有广泛的应用前景。目前,电解水产氢是一种重要的制备高纯氢气的方法。为了高效的电解水产氢,研究者开发出多种电催化析氢材料,主要包括过渡金属的硫化物、氧化物、碳化物和磷化物等四类非贵金属材料。本文综述了上述四类材料的最新研究进展,并根据存在的问题提出展望,以期使该类材料能够尽快大规模应用。     

硫化物催化剂电催化析氢性能的研究进展

当今社会,清洁能源取代化石原料能源是一种主流趋势,制备清洁能源成为当下的热门话题。氢气作为优良的清洁能源,具有可再生、绿色环保、来源广泛等优点,成为制取的首要目标。常见的高效制氢方法是电催化析氢法,实验室中传统电析氢催化剂主要以贵金属为材料,因贵金属数量少且价格贵,以非贵金属材料硫化物代替价格昂贵的贵金属材料为切入点进行研究制取硫化物析氢催化剂,然而硫化物析氢催化剂相比于贵金属催化剂有着导电性能差、易聚团等缺点,针对以上问题进行研究,通过合成多种硫化物,对他们进行电化学和结构等测试,从多方面考虑制得析氢性能的优良和稳定性更好的催化剂,为制得电解析氢催化剂提供有效的理论指导。     

过渡金属磷化物的改性方法及其在电化学析氢中的应用

过渡金属磷化物催化活性高、稳定性好，是电催化析氢的良好催化剂。然而，实现过渡金属磷化物在电解水制氢领域的大规模应用，还需要进一步提升其催化性能。本文以过渡金属磷化物的组成变化为出发点，从金属/磷（M/P）化学计量比的角度对过渡金属磷化物的性能进行了总结，介绍了其常见的制备方法，详细综述了元素掺杂、构造缺陷、构建界面工程、耦合炭材料、调控微观结构、改善材料浸润性等改性方法对过渡金属磷化物电催化制氢性能的影响。最后在新型磷源的开发、测试标准化、晶面调控等方面对过渡金属磷化物的发展趋势进行了展望。     

石墨烯材料电催化析氢活性高

<正>中国科学技术大学陈乾旺教授课题组近日以贵金属铱掺杂的金属有机框架材料作为前驱体,一步煅烧制备了氮掺杂的类石墨烯层包裹铱钴合金核壳结构材料,在酸性电解质析氢反应中表现出高活性和高稳定性。该工作为今后寻找更为廉价、高效的电催化析氢催化剂提供了新思路。近年来,电解水制氢受到学术界广泛关注,     

电催化氧气析出非贵金属催化剂的研究进展

电催化氧气析出反应是金属-空气电池充电过程和电催化分解水阳极的关键反应,对提高能量储存和转换效率、高效利用可再生清洁能源、缓解能源危机和环境污染具有重要作用。文章首先简要介绍了电催化氧气析出反应基本过程,随后综述了近年来用于电催化氧气析出反应的非贵金属催化剂的研究进展,重点讨论了过渡金属氧化物、过渡金属氢氧化物以及碳材料等非贵金属催化剂的研发情况。对这些催化剂的合成、结构及氧气析出催化性能进行了详细分析,也对这些催化剂的发展方向进行了简单分析。文章最后认为,新合成技术、新催化材料的发展以及氧气析出催化反应机理的阐明对发展高性能电催化氧气析出非贵金属催化剂将会起到极大的推动作用。     

钌基碱性电解水制氢催化剂研究进展

碱性电解水具有操作易实现、设备费用低和寿命长的特点,是目前应用最广泛的将可再生资源转化为氢能的技术。但电解水存在能耗高的问题,因此需要高效催化剂提高能量转化效率。钌具有与铂相近的金属-氢键强度,是极具前景的制氢催化剂。综述了近年来钌基催化剂的制备及其碱性电解水制氢反应的最新研究进展。与廉价过渡金属材料相比,钌基催化剂具有优异的电化学活性和稳定性,是一种很有前景的析氢材料。以目前主要研究的钌金属及其合金、钌基磷化物、钌基硫化物、钌基硒化物为代表,分别进行了简要的介绍和评价,最后提出了钌基电催化剂在制氢应用中存在的问题和未来的发展方向。     

Polymer electrolyte membrane water electrolysis: status of technologies and potential applications in combination with renewable power sources

Technological improvements in polymer electrolyte membrane water electrolysers (PEMWEs) are promoted by their exciting possibilities to operate with renewable power sources. In this paper, a synopsis of the research efforts concerning with the development of electrocatalysts, polymer electrolytes and stack hardware components is presented. The most challenging problem for the development of PEMWEs is the enhancement of oxygen evolution reaction rate. At present, there are no practical alternatives to noble metal-based oxide catalysts such as IrO₂ and RuO₂. As well as carbon supported Pt nanoparticles are the benchmark cathode catalysts for hydrogen evolution. High noble metal loading on the electrodes and the use of perfluorosulfonic membranes significantly contribute to the cost of these devices. Critical areas include the design of appropriate mixed electrocatalysts and their dispersion on low cost Ti-oxide like supports to increase catalyst utilization. Moreover, the development of alternative membranes with enhanced mechanical properties for high pressure applications, proper conductivity and reduced gas cross-over is strongly required. This latter aspect is also addressed by the development of proper recombination catalysts. The development of anodic mixed non-noble transition metal oxides with spinel or perovskite structure and proper resistance to chemical degradation in the acidic environment and electrochemical corrosion is also an active area of research. Similarly, efforts are also being addressed to Pd and Ru based cathode formulations with cheaper characteristics than Pt. Whereas, concerning with stack hardware, cost reduction may be addressed by replacing Ti-based diffusion media and bipolar plates with appropriate and cost-effective stainless steel materials with enhanced resilience to chemical and electrochemical corrosion. Regarding the combination with renewable power sources, PEM electrolysers can find suitable applications for peak shaving in integrated systems grid connected or in grid independent operating conditions where hydrogen generated through electrolysis is stored and then via fuel cell converted back to electricity when needed or used to refill fuel cell-based cars. Hydrogen is the most promising clean energy carrier to accomplish the sustainable production of energy and a synergy among hydrogen, electricity and renewable energy sources is highly desired.     

Structural engineering of transition metal-based nanostructured electrocatalysts for efficient water splitting

Water splitting is a highly promising approach for the generation of sustainable, clean hydrogen energy. Tremendous efforts have been devoted to exploring highly efficient and abundant metal oxide electrocatalysts for oxygen evolution and hydrogen evolution reactions to lower the energy consumption in water splitting. In this review, we summarize the recent advances on the development of metal oxide electrocatalysts with special emphasis on the structural engineering of nanostructures from particle size, composition, crystalline facet, hybrid structure as well as the conductive supports. The special strategies relay on the transformation from the metal organic framework and ion exchange reactions for the preparation of novel metal oxide nanostructures with boosting the catalytic activities are also discussed. The fascinating methods would pave the way for rational design of advanced electrocatalysts for efficient water splitting.     

可再生能源电解制氢技术及催化剂的研究进展

氢能是一种清洁、高效的二次能源,是构建未来清洁社会的重要支撑。在众多制氢技术中,利用可再生能源产生电能,并通过电解水制备高纯度氢气是最具潜力的制氢路线之一。本文在介绍三种电解水制氢技术及核心部件的基础上,重点讨论了电解水析氢催化剂,特别是过渡金属基电催化剂及单原子催化剂的研究进展。本文最后对可再生能源发电与电解水制氢技术的耦合进行了分析与讨论,简述了现阶段国内外基于可再生能源发电制氢项目的开发进展。文章指出,随着电力成本下降,高效、稳定、经济的析氢催化剂的开发,可再生能源发电制氢将成为解决能源消纳、加速氢能产业化进程、最终实现我国向低碳清洁能源转型的重要途径。     

Co anchored on porphyrinic triazine-based frameworks with excellent biocompatibility for conversion of CO2 in H2-mediated microbial electrosynthesis

Microbial electrosynthesis is a promising alternative to directly convert CO₂ into long-chain compounds by coupling inorganic electrocatalysis with biosynthetic systems. However, problems arose that the conventional electrocatalysts for hydrogen evolution may produce extensive by-products of reactive oxygen species and cause severe metal leaching, both of which induce strong toxicity toward microorganisms. Moreover, poor stability of electrocatalysts cannot be qualified for long-term operation. These problems may result in poor biocompatibility between electrocatalysts and microorganisms. To solve the bottleneck problem, Co anchored on porphyrinic triazine-based frameworks was synthesized as the electrocatalyst for hydrogen evolution and further coupled with Cupriavidus necator H16. It showed high selectivity for a four-electron pathway of oxygen reduction reaction and low production of reactive oxygen species, owing to the synergistic effect of Co–N_x modulating the charge distribution and adsorption energy of intermediates. Additionally, low metal leaching and excellent stability were observed, which may be attributed to low content of Co and the stabilizing effect of metalloporphyrins. Hence, the electrocatalyst exhibited excellent biocompatibility. Finally, the microbial electrosynthesis system equipped with the electrocatalyst successfully converted CO₂ to poly-β-hydroxybutyrate. This work drew up a novel strategy for enhancing the biocompatibility of electrocatalysts in microbial electrosynthesis system.     

质子交换膜电解水制氢技术的发展现状及展望

氢能是支撑起智能电网和可再生能源发电规模化的最佳能源载体,而电解水制氢是实现制氢规模化的重要途径。在多种电解水制氢技术中,质子交换膜电解水技术由于具备电流密度大、产氢纯度高、响应速度快等优势,吸引了科学界和工业界的广泛重视。本文首先介绍了质子交换膜电解池的结构组成以及各组成的主要作用,对比分析了碱性电解池、固体氧化物电解池与质子交换膜电解池的技术差异,并结合电解水析氢反应以及析氧反应的机理阐释,分别介绍了两步半反应的常用催化剂;然后,从最初的实验室研究阶段到目前兆瓦级别的质子交换膜电解水系统,回顾了该技术的发展历程以及应用现状;其次,从制氢成本、电堆性能及电堆寿命等多角度分析目前该技术面临的瓶颈问题;最后,根据质子交换膜电解池的技术优势,并针对上游间歇性可再生能源的需求以及和下游产业的联合应用,对其未来前景进行了展望。     

Recent advance in transition metal oxide-based materials for oxygen evolution reaction electrocatalysts

Using renewable energy to electrolyze water to produce hydrogen is the only way to realize a green hydrogen economy. At present, the large-scale application of this technology is encumbered by the relatively low activity and stability of oxygen evolution reaction (OER) electrocatalysts. The use of cost-effective catalysts can significantly reduce the overpotential of oxygen evolution and improve the economics and power conversion efficiency of the hydrogen production process from electrolysis of water. Among the various candidates, the transition metal oxide-based (TMOs) materials show great prospects and receive ever-increasing research interests because of their diversified surface/bulk structures, natural enrichment, easy accessibility and environmental friendliness. In this review, the latest tactics aiming at enhancing activity via increasing the accessible active sites and promoting intrinsic activity have been summarized. In addition, with special emphasis on the long-term stability, the up-to-data strategies for elevating the stability are introduced. Finally, conclusions and perspectives are also presented.     

过渡金属氧化物催化析氧反应研究进展

利用可再生能源电解水制氢,是实现绿色氢能经济的必由之路。现阶段,电解水过程的阳极析氧反应过电位较高,催化剂性能不稳定,制约着该技术的工业化应用。使用经济高效的催化剂,可显著降低析氧过电位,提高电解水制氢过程的经济性和电能转化效率。在各类析氧催化剂材料中,过渡金属氧化物(TMOs)由于晶体结构多样、储量丰富、环境友好、易于制备以及活性较高等优点,受到了越来越多的关注。本文从活性和稳定性出发,总结分析了近年来过渡金属氧化物催化析氧反应的研究进展,并对其未来的发展提出了建议与展望。     

H2O2基燃料电池阴极催化剂的研究进展

本文综述了燃料电池中H2O2电还原催化剂的研究,其主要集中在贵金属、过渡金属的大环化合物、酶以及非贵金属氧化物,其中研究非贵金属氧化物作为H2O2电还原的催化剂将是未来发展的方向.     

电解海水催化剂的设计与改性

电解海水是一种可再生、可持续、低成本且节约淡水资源的氢气生产方案。因此,针对天然海水或盐水电解质的析氢反应（HER）和析氧反应（OER）,设计开发高效、稳定的电催化剂具有良好的应用前景。为了深入了解海水电解所面临的现状和挑战,本文对电催化分解海水催化剂的设计思路与改性方法进行了系统的回顾和总结。首先详细讨论了电解海水中析氢反应、析氧反应、析氯反应的基本原理。随后对最近报道的在海水中能够稳定运行的HER和OER电催化剂进行了汇总和分析。针对阴极催化剂,分别概述了高效贵金属基电催化剂和低成本过渡金属基电催化剂。针对阳极催化剂,主要讨论了取得较大进展的镍基催化剂,随后对镍基之外的其他电催化剂进行对比补充。文章最后对电解海水催化剂目前所面临的挑战和发展方向进行了总结和展望,基于现有分析认为,在未来的研究中需要进一步探索新型电解海水催化剂的种类和结构,开发更高效稳定的阴极和具有更高OER选择性的阳极电催化剂,以满足分解海水电催化剂工业化应用的要求。