水电解制氢非贵金属催化剂的研究进展

氢能作为零碳排放能源是被公认的最清洁能源之一,如何有效可持续地产氢是未来人类步入氢能经济首先要解决的问题。电解水技术基于电化学分解水的原理,利用可再生电能或太阳能驱动水分解为氢气和氧气,被认为是最有前途和可持续性的产氢途径。然而,无论是光解水还是电解水,均需要高活性、高稳定性的非贵金属氢析出和氧析出催化剂以使水电解反应经济节能。本文介绍了我们研究所近三年在水电解方面的研究进展,其中着重介绍了：（ⅰ）氢析出催化剂,包括利用低温磷化过渡金属（氢）氧化物的方法制备过渡金属磷化物,同时过渡金属硫化物、硒化物以及碳化物等均被成功合成并被应用为有效的阴极析氢催化剂;（ⅱ）氧析出催化剂,主要包括金属磷化物、硫化物、氧化物/氢氧化物等;（ⅲ）双功能催化剂,主要包括过渡金属磷化物、硒化物、硫化物等。最后,总结展望了发展水电解非贵金属催化剂所面临的挑战与未来发展方向。     

Heteroatom‐doped MoSe2 Nanosheets with Enhanced Hydrogen Evolution Kinetics for Alkaline Water Splitting

Electrochemical water splitting for hydrogen generation is a vital part for the prospect of future energy systems, however, the practical utilization relies on the development of highly active and earth‐abundant catalysts to boost the energy conversion efficiency as well as reduce the cost. Molybdenum diselenide (MoSe₂) is a promising nonprecious metal‐based electrocatalyst for hydrogen evolution reaction (HER) in acidic media, but it exhibits inferior alkaline HER kinetics in great part due to the sluggish water adsorption/dissociation process. Herein, the alkaline HER kinetics of MoSe₂ is substantially accelerated by heteroatom doping with transition metal ions. Specifically, the Ni‐doped MoSe₂ nanosheets exhibit the most impressive catalytic activity in terms of lower overpotential and larger exchange current density. The density functional theory (DFT) calculation results reveal that Ni/Co doping plays a key role in facilitating water adsorption as well as optimizing hydrogen adsorption. The present work paves a new way to the development of low‐cost and efficient electrocatalysts towards alkaline HER.     

水电解析氢低贵/非贵金属催化剂的研究进展

氢气作为能量载体的氢能技术由于其清洁性、高能量密度等优势已获得越来越多的青睐与关注. 其中,可持续的产氢技术是未来氢能经济发展的必要先决条件. 通过可再生资源电力驱动的电解水技术是支持氢能经济可持续发展的重要途径,高活性、低成本的析氢催化剂的开发利用是提高水电解技术效率并降低其成本的关键因素. 本文主要介绍了近年来包括低铂催化剂和金属硫化物、金属磷化物、金属硒化物等非铂过渡金属催化剂在析氢方面的研究进展,详细讨论了析氢反应的催化性能、合成方法以及结构?鄄催化性能的关系,最后总结展望了水电解低铂及非铂过渡金属催化剂在未来发展过程中所面临的机遇与挑战.     

Low-Temperature Direct Electrochemical Methanol Reforming Enabled by CO-Immune Mo-Based Hydrogen Evolution Catalysts

Hydrogen storage in the form of intermediate artificial fuels such as methanol is important for future chemical and energy applications, and the electrochemical regeneration of hydrogen from methanol is thermodynamically favorable compared to direct water splitting. However, CO produced from methanol oxidation can adsorb to H₂-evolution catalysts and drastically reduce activity. In this study, we explore the origins of CO immunity in Mo-containing H₂-evolution catalysts. Unlike conventional catalysts such as Pt or Ni, Mo-based catalysts display remarkable immunity to CO poisoning. The origin of this behavior in NiMo appears to arise from the apparent inability of CO to bind Mo under electrocatalytic conditions, with mechanistic consequences for the H₂-evolution reaction (HER) in these systems. This specific property of Mo-based HER catalysts makes them ideal in environments where poisons might be present.     

Research Progress in Hydrogen Evolution Low Noble/Non-Precious Metal Catalysts of Water Electrolysis北大核心CSCD

Hydrogen energy technology with hydrogen as an energy carrier is gaining more and more attention due to its cleanliness and high energy density.Hydrogen fuel cell vehicles have been listed as one of the ultimate energy technologies in the 21st century.Among them, sustainable hydrogen production technology is a necessary prerequisite for the future development of hydrogen energy economy.Electrolyzed water technology driven by renewable resources represents an important way to support the sustainable development of hydrogen energy economy.The development and utilization of high activity, low cost hydrogen evolution catalysts is a key factor in improving the efficiency and reducing the cost of water electrolysis technology.This paper mainly introduces the recent research progress of hydrogen evolution catalysts including low platinum catalysts and non-platinum transition metal catalysts such as metal sulfides metal phosphides, metal selenides, etc; catalytic properties, synthesis methods, and structure-catalytic properties.Finally, the advantages and challenges of water electrolysis low platinum and non-platinum transition metal catalysts in the future development are prospected. © 2018 Chinese Chemical Society. All rights reserved.     

Photocatalytic hydrogen production

The efficient storage of solar energy in chemical fuels, such as hydrogen, is essential for the large-scale utilisation of solar energy systems. Recent advances in the photocatalytic production of H(2) are highlighted. Two general approaches for the photocatalytic hydrogen generation by homogeneous catalysts are considered: HX (X = Cl, Br) splitting involving both proton reduction and halide oxidation via an inner-sphere mechanism with a single-component catalyst; and sensitized H(2) production, employing sacrificial electron donors to regenerate the active catalyst. Future directions and challenges in photocatalytic H(2) generation are enumerated.     

非晶非贵金属催化剂的研究进展及展望

近年来电解水产氢作为一种具有前景的制备及储存可再生能源的方法受到了各界的广泛关注.在此过程中,电解水催化剂是提高能源转换效率的关键.优秀的催化剂应具备高催化活性、高稳定性、低成本以及可大规模生产等性质.科研工作者对电解水的两部分反应,即析氢反应以及析氧反应均进行了广泛及深入的研究.目前,贵金属催化剂,如铂基、钌基催化剂的催化活性要高于其他元素催化剂,但由于其价格昂贵,储量较少使得贵金属催化剂无法得到大规模应用,因此发展非贵金属催化剂对绿色能源的发展具有重要意义.一般而言,催化剂的结晶度越高,其催化活性越好,而近年来非晶催化剂以其更高的催化活性位密度也越来越受到人们的重视.同时,非晶催化剂的成分更加灵活,相比晶体催化剂来说非晶催化剂可以在更大范围内对成分进行调节.此外,非晶催化剂的制备通常都在较为温和的反应条件下进行,这也能够降低生成成本,促进其工业化发展.在这篇综述里我们介绍了电解水反应的基本原理,总结了近期非晶析氢、析氧以及双功能催化剂的研究进展.并随后探讨了电解水反应目前的难点并对非晶催化剂的制备进行了展望.     

Nanocatalysts for Solar Water Splitting and a Perspective on Hydrogen Economy

In this review article, nanocatalysts for solar hydrogen production are the focus of discussion as they can contribute to the development of sustainable hydrogen production in order to meet future energy demands. Achieving this task is subject of scientific aspirations in the field of photo‐ and photoelectrocatalysis for solar water splitting where systems of single catalysts or tandem configurations are being investigated. In search of a suitable catalyst, a number of crucial parameters are laid out which need to be considered for material design, in particular for nanostructured materials that provide exceptional physical and chemical properties in comparison to their bulk counterparts. Apart from synthetic approaches for nanocatalysts, key parameters and properties of nanostructured photocatalysts such as light absorption, charge carrier generation, charge transport, separation and recombination, and other events that affect nanoscale catalysts are discussed. To provide a deeper understanding of these key parameters and properties, their contribution towards existing catalyst systems is evaluated for photo‐ and photoelectrocatalytic solar hydrogen evolution. Finally, an insight into hydrogen production processes is given, stressing the current development of sustainable hydrogen sources and presenting a perspective towards a hydrogen‐based economy.     

Nature-driven photochemistry for catalytic solar hydrogen production: a Photosystem I-transition metal catalyst hybrid

Solar energy conversion of water into the environmentally clean fuel hydrogen offers one of the best long-term solutions for meeting future energy demands. Nature provides highly evolved, finely tuned molecular machinery for solar energy conversion that exquisitely manages photon capture and conversion processes to drive oxygenic water-splitting and carbon fixation. Herein, we use one of Nature's specialized energy-converters, the Photosystem I (PSI) protein, to drive hydrogen production from a synthetic molecular catalyst comprised of inexpensive, earth-abundant materials. PSI and a cobaloxime catalyst self-assemble, and the resultant complex rapidly produces hydrogen in aqueous solution upon exposure to visible light. This work establishes a strategy for enhancing photosynthetic efficiency for solar fuel production by augmenting natural photosynthetic systems with synthetically tunable abiotic catalysts.     

Carbon‐Based Metal‐Free Catalysts for Electrocatalysis beyond the ORR

Besides their use in fuel cells for energy conversion through the oxygen reduction reaction (ORR), carbon‐based metal‐free catalysts have also been demonstrated to be promising alternatives to noble‐metal/metal oxide catalysts for the oxygen evolution reaction (OER) in metal–air batteries for energy storage and for the splitting of water to produce hydrogen fuels through the hydrogen evolution reaction (HER). This Review focuses on recent progress in the development of carbon‐based metal‐free catalysts for the OER and HER, along with challenges and perspectives in the emerging field of metal‐free electrocatalysis.     

提升二维材料的电催化析氢和光催化析氢性能的策略

世界能源危机问题和环境问题日益突出,寻找低廉、易得且能够替代化石的清洁能源是目前研究的热点.氢气具有可再生性、安全、高能量密度、环境友好型等优点,因而成为替代化石燃料的首选.在众多途径中,电催化产氢和光催化产氢是目前应用较广且比较成熟的方法,其工艺过程简单、无污染,但由于效率较低或生产成本较高等因素,其大规模应用受到一...     

MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction

Advanced materials for electrocatalytic and photoelectrochemical water splitting are central to the area of renewable energy. In this work, we developed a selective solvothermal synthesis of MoS(2) nanoparticles on reduced graphene oxide (RGO) sheets suspended in solution. The resulting MoS(2)/RGO hybrid material possessed nanoscopic few-layer MoS(2) structures with an abundance of exposed edges stacked onto graphene, in strong contrast to large aggregated MoS(2) particles grown freely in solution without GO. The MoS(2)/RGO hybrid exhibited superior electrocatalytic activity in the hydrogen evolution reaction (HER) relative to other MoS(2) catalysts. A Tafel slope of ～41 mV/decade was measured for MoS(2) catalysts in the HER for the first time; this exceeds by far the activity of previous MoS(2) catalysts and results from the abundance of catalytic edge sites on the MoS(2) nanoparticles and the excellent electrical coupling to the underlying graphene network. The ～41 mV/decade Tafel slope suggested the Volmer-Heyrovsky mechanism for the MoS(2)-catalyzed HER, with electrochemical desorption of hydrogen as the rate-limiting step.     

Hydrogenase enzymes: Application in biofuel cells and inspiration for the design of noble-metal free catalysts for H2 oxidation

While hydrogen is often considered as a promising energy vector and an alternative to fossil fuels, the rise of the hydrogen economy is ever and ever postponed. This is mainly due to the high costs of the materials required for the elaboration of fuel cells, these wonderful systems that release the energy contained in the H₂ molecule in the form of electrical power. Indeed, scarce and precious platinum is required as a catalyst at both electrodes of fuel cells. A solution may be found in nature with metalloenzymes involved in hydrogen metabolism, called hydrogenases. These natural catalysts can be used directly in biofuel cells or serve as an inspiration to chemists for the elaboration of bio-inspired electrocatalytic materials.     

Influence of reduction energy match among CuO species in CuO-CeO2 catalysts on the catalytic performance for CO preferential oxidation in excess hydrogen

In the present study, we have investigated the reducibility of CuO species on CuO-CeO2 catalysts and the influence of CuO species on the catalytic performance for CO preferential oxidation (CO PROX) in excess hydrogen. It is revealed that the smaller the difference of reduction temperature (denoted as ?T) for two adjacent CuO species is, the higher the catalytic activity of CuO-CeO2 for the PROX in excess hydrogen may be obtained. It means that if the reduction energy of Cu0-Cu2+ pairs matched better, the reduction-oxidation recycle of Cu0-Cu2+ pairs would go on more easily, then the transferring energy of Cu0-Cu2+ pairs would be lesser. Therefore, the CuO-CeO2 catalysts will be largely improved in their catalytic performance if the different CuO species on the catalysts have matched the reduction energy, which would allows them to cooperate effectively.     

Efficient Hydrogen Evolution Electrocatalysis Using Cobalt Nanotubes Decorated with Titanium Dioxide Nanodots

TiO₂ Co nanotubes decorated with nanodots (TiO₂ NDs/Co NSNTs‐CFs) are reported as high‐performance earth‐abundant electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. TiO₂ NDs/Co NSNTs can promote water adsorption and optimize the free energy of hydrogen adsorption. More importantly, the absorbed water can be easily activated in the presence of the TiO₂–Co hybrid structure. These advantages will significantly promote HER. TiO₂ NDs/Co NSNTs‐CFs as electrocatalysts show a high catalytic performance towards HER in alkaline solution. This study will open up a new avenue for designing and fabricating low‐cost high‐performance HER catalysts.     

Artificial photosynthesis: from molecular catalysts for light-driven water splitting to photoelectrochemical cells

Photosynthesis has been for many years a fascinating source of inspiration for the development of model systems able to achieve efficient light-to-chemical energetic transduction. This field of research, called "artificial photosynthesis," is currently the subject of intense interest, driven by the aim of converting solar energy into the carbon-free fuel hydrogen through the light-driven water splitting. In this review, we highlight the recent achievements on light-driven water oxidation and hydrogen production by molecular catalysts and we shed light on the perspectives in terms of implementation into water splitting technological devices.     

Platinum Group Metal–free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells

Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low‐grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost‐effective. A variety of noble‐metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS₂, carbon‐based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications.     

Recent Progress of Transition Metal Compounds as Electrocatalysts for Electrocatalytic Water Splitting

Hydrogen has enormous commercial potential as a secondary energy source because of its high calorific value, clean combustion byproducts, and multiple production methods. Electrocatalytic water splitting is a viable alternative to the conventional methane steam reforming technique, as it operates under mild conditions, produces high-quality hydrogen, and has a sustainable production process that requires less energy. Electrocatalysts composed of precious metals like Pt, Au, Ru, and Ag are commonly used in the investigation of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Nevertheless, their limited availability and expensive cost restrict practical use. In contrast, electrocatalysts that do not contain precious metals are readily available, cost-effective, environmentally friendly, and possess electrocatalytic performance equal to that of noble metals. However, considerable research effort must be devoted to create cost-effective and high-performing catalysts. This article provides a comprehensive examination of the reaction mechanism involved in electrocatalytic water splitting in both acidic and basic environments. Additionally, recent breakthroughs in catalysts for both the hydrogen evolution and oxygen evolution reactions are also discussed. The structure-activity relationship of the catalyst was deep-going discussed, together with the prospects of current obstacles and potential for electrocatalytic water splitting, aiming at provide valuable perspectives for the advancement of economical and efficient electrocatalysts on an industrial scale.