过渡金属氧化物析氧催化都是通过氧氢氧化物实现的吗?（英文）

本文首先简单回顾了电解水的发展历史以及碱性和酸性条件下电解水的电极材料特点.对于碱性条件下的电解水,电极材料以过渡金属氧化物为主.近年来,人们对于过渡金属氧化物的析氧反应开展了大量的研究,特别关注钙钛矿、尖晶石、氧氢氧化物等催化剂.析氧反应条件苛刻,一些氧化物催化剂会发生表面重构,转化为过渡金属氧氢氧化物.因此,对这些氧化物来讲,真正的催化剂表面是一个氧氢氧化物的表面.另一方面,一些氧化物在析氧反应中表现出较强的稳定性,一般认为这些氧化物的表面不会发生重构,因而没有氧氢氧化物的生成.一些已知的基于氧化物结构的活性描述参数也对该观点提供了实验和理论支持.最后,本文提出尚待回答的一个问题:在析氧反应中是否所有的过渡金属氧化物都会发生表面重构而生成一个氧氢氧化物的表面?不管以上问题的答案是什么,该如何设计预催化剂实现重构后的高活性表面将成为未来关注的热点之一.     

Highly active oxide photocathode for photoelectrochemical water reduction

A clean and efficient way to overcome the limited supply of fossil fuels and the greenhouse effect is the production of hydrogen fuel from sunlight and water through the semiconductor/water junction of a photoelectrochemical cell, where energy collection and water electrolysis are combined into a single semiconductor electrode. We present a highly active photocathode for solar H(2) production, consisting of electrodeposited cuprous oxide, which was protected against photocathodic decomposition in water by nanolayers of Al-doped zinc oxide and titanium oxide and activated for hydrogen evolution with electrodeposited Pt nanoparticles. The roles of the different surface protection components were investigated, and in the best case electrodes showed photocurrents of up to -7.6 mA cm(-2) at a potential of 0 V versus the reversible hydrogen electrode at mild pH. The electrodes remained active after 1 h of testing, cuprous oxide was found to be stable during the water reduction reaction and the Faradaic efficiency was estimated to be close to 100%.     

Recent advances in visible light-driven water oxidation and reduction in suspension systems

In order to solve the shortage of sustainable energy and the related concern about combustion of fossil fuels, converting the most abundant solar energy into chemical fuels becomes one of the most promising choices to provide the everlasting and environmentally friendly energy vector along with the minimum impact on environment. Among the methods of converting solar energy into chemical fuels, there is a significant interest in the renewable hydrogen production by photocatalysts from abundant water under visible light irradiation. Therefore, the development of efficient photocatalysts for water reduction and oxidation in a suspension system is the footstone for the development of solar energy conversion. In this review, the fundamental theory of photocatalysis and key factors affecting photocatalysis will be introduced first. Then the new materials development covering inorganic materials (oxides, nitrides and sulfides), carbon-based photocatalysts, and semiconductor-coordination compound photocatalysts developed over the past 10?years will be addressed with discussion about dominating factors in the photochemical process. This review would provide a comprehensive reference to exploring the efficient and novel materials working for the solar energy conversion to affordable and sustainable fuels. Finally, the perspective of the technology is also discussed.     

Using biomass as an energy source with low CO2 emissions

This work deals with the carbon dioxide cycle and emissions from biomass incineration under a hydrogen production context. It is proposed to use the thermal energy obtained by biomass combustion to produce water steam, which afterwards would be converted into hydrogen by high temperature electrolysis (HTE). In France, the thermal energy potential from nonvalorised biomass reaches almost 6.5 Mtep. In this study, the potential avoided carbon emissions are quantified as well as the feasible hydrogen production capacity based on the steam supplied by the incineration units. Results show that carbon consumption in hydrogen production by steam methane reforming (SMR) or biomass incineration–HTE process is almost equivalent between both processes. However, the hydrogen produced by the biomass incineration–HTE process used to fuel vehicles, would lead to a decrease of 135 Mt of carbon from fossil origins yearly, in contrast to SMR.     

Fundamental aspects and recent advances in transition metal nitrides as electrocatalysts for hydrogen evolution reaction: A review

With increasing human population, sustainable energy production has become one of the most persistent and significant problems of the current century. Hydrogen is considered to be the best clean fuel for future energy requirements. As a substitute of fossil fuels, hydrogen is readily provided by an electrocatalytic hydrogen evolution reaction that splits water molecules. Conventional electrocatalysts based on noble metals are scarce and considerably expensive for large-scale hydrogen production, necessitating the search for low-cost earth abundant alternatives. In this context, transition metal nitrides have gained considerable attention as competent electrocatalytic materials for water splitting. This review presents recent advancements and progress on transition metal nitrides as efficient and cost-effective electrocatalysts for hydrogen production. After overviewing the fundamental aspects of the hydrogen evolution reaction (HER), the review discusses various synthetic strategies for developing transition metal nitrides. Discussed herein are titanium nitrides, vanadium nitrides, iron nitrides, nickel nitrides, molybdenum nitrides, tungsten nitrides, and their composite electrocatalysts employed in HER applications. Some design viewpoints for improving the electrocatalytic activity are systematically proposed. Finally, the review discusses challenges and future perspectives for the advancement of non-noble metal-based electrocatalysts.     

基于电催化析氧反应的非贵金属催化剂研究进展

在全球变暖和能源危机的背景下，能源问题已成为全球各国战略安全的重要组成部分。氢能作为可持续的新型可再生清洁能源，对缓解全球性能源短缺具有重要意义。在众多制氢候选方案中，电解水制备氢气被认为是最可靠、最可行的途径之一。但在电解过程中，反应动力学极为迟缓的阳极析氧反应(Oxygen evolution reaction,OER)严重制约着整体反应效率。因此，开发成本相对低廉、催化剂性能优异、耐久性好的高效OER电催化剂，从而提高电解水制氢工艺技术的能源转换效果受到了广泛关注。本文首先简要阐述了析氧反应的反应机制及其性能的评价参数，接着对非贵金属催化剂的研究进行分类讨论，并列举了提高催化性能的策略和方法，最后对设计新型催化剂进行展望。     

Recent development of perovskite oxide-based electrocatalysts and their applications in low to intermediate temperature electrochemical devices

As a consequence of the depletion of fossil fuels and an increasing population, the global energy crisis has driven researchers to explore innovative energy storage and conversion (ESC) devices, such as fuel cells, electrolyzers and chemical looping systems. In order to enhance the energy conversion efficiency of these electrochemical devices, high performance and stable electrocatalysts are essential to accelerate the sluggish electrochemical kinetics, e.g. oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and redox reaction. In recent years, as cost-effective and high-efficient catalysts, perovskite oxides have attracted much attention. In addition, the potential of perovskite electrocatalysts may be further boosted due to their flexible composition and tunable electronic structures. This review provides the readers with a comprehensive understanding and updated information of improvements towards the electrocatalytic performances of perovskite oxides. It will focus on research papers regarding low to intermediate temperature electrochemical devices, e.g., water splitting, fuel cells, chemical looping technology and three-way catalysis (TWC) published over the last five years. Various design strategies for optimizing the conductivity and catalytic activity of perovskite are discussed in detail. In the end, this review discusses challenges for the future researches in regard to perovskite based electrocatalysts.     

The rationality of low carbon technologies

Combustion of fossil fuels increases permanently the carbon content of the fast carbon cycle consisting of atmosphere,land and surface ocean.The carbon residence times in these reservoirs are relatively low in the order of some years.Hower,the carbon residence time in the whole fast cycle is in the order of 2,000 years.This means the final storage problem of fossil energy use is in the same order as that of nuclear energy use. There are two other main driving forces for a continuous decarbonisation of the world energy system.The first one is the shortening of raw materials,an the second one is the greenhous gas effect of carbon dioxide with the risk of climate change. Based on the "molecular fingerprints"of various fossil fuels a new quantity.the "energetic carbon efficiency"can be derived.This quantity favours methane(natural gas)more than any other fossil fuel.E.g.,methane is two times more efficient than lignite or hard coaL Therefore,the future role of this energy carrier will be discussed more in detail. Carbon capture and storage(CCS)is not a convincing concept and therefore it cannot be considered as a responsible excuse for new coal fired power stations.A reasonable way out may be the carbon moratorium.This means a thermal splitting of methane into carbon and hydrogen.Only the hydrogen is used as a fuel whereas the carbon is deposited in the earth,because storage of carbon is much safer than storage of carbon dioxide. Very often biofuels are considered as a sustainable option.Critical arguments are presented against the meander of biofuels. Negative climate implications and very low efficiencies are serious arguments against these teehnolgies.Even the fashionable new hope for bioenergy from algea farms has no rational fundament. A long-time sustainable energy system requires not only low carbon but zero carbon technologies.This means solar energy in all kinds of its appearance(water power,wind,solar heat and photovoltaics).However these kinds of energy require new energy storage technologies.Various storage technologies will be discussed with a special focus on electrochemical batteries and electromobility. All of these new energy technologies are not able to remove any carbon from the fast carbon cycle.Therefore,some prominent concepts of climate engineering will be introduced.     

Hydrogen energy

The problem of anthropogenically driven climate change and its inextricable link to our global society's present and future energy needs are arguably the greatest challenge facing our planet. Hydrogen is now widely regarded as one key element of a potential energy solution for the twenty-first century, capable of assisting in issues of environmental emissions, sustainability and energy security. Hydrogen has the potential to provide for energy in transportation, distributed heat and power generation and energy storage systems with little or no impact on the environment, both locally and globally. However, any transition from a carbon-based (fossil fuel) energy system to a hydrogen-based economy involves significant scientific, technological and socio-economic barriers. This brief report aims to outline the basis of the growing worldwide interest in hydrogen energy and examines some of the important issues relating to the future development of hydrogen as an energy vector.     

ZnO增强MxCo3-xO4电催化析氧性能研究

氢能因热值高、燃烧产物无污染等优良特性,成为目前新型能源研究的焦点,有望成为化石能源的理想替代品。电催化水分解作为最具前景的氢气制备方法,包含两个半反应:析氧反应(OER)和析氢反应(HER)。其中OER目前主要采用贵金属作为催化剂,但其高成本极大地限制了电催化产氢的工业化。基于Co 3O 4的Co基掺杂氧化物具有成本低廉、催化活性高且稳定性强等优良特性。目前对于Co基掺杂氧化物的研究主要集中于探究掺杂不同金属元素(Zn,Ni,Fe等)对其催化活性的影响,极少研究掺杂惰性氧化物对其催化活性的影响。合成了一种CoFeNiZn复合氧化物,且具有优良的电催化活性和稳定性。在1 mol/L KOH的电解液中,10 mA/cm 2的电流密度下,CoFeNiZn复合氧化物过电势(η10)为310 mV,塔菲尔斜率(Tafel slope)为40 mV/dec,相比原始CoFeNi氧化物(η10为400 mV)过电势降低了90 mV。CoFeNiZn催化剂催化性能的提高主要是由于以惰性ZnO作为基质可有效地分散催化活性物质,并充分暴露CoFeNi氧化物的催化活性位点。这一基于催化材料掺杂非活性物质提高催化剂催化活性的发现可以为现有催化剂开发提供新的思路。     

Recent Advances in Conjugated Polymers for Visible-Light-Driven Water Splitting

With the ambition of solving the challenges of the shortage of fossil fuels and their associated environmental pollution, visible-light-driven splitting of water into hydrogen and oxygen using semiconductor photocatalysts has emerged as a promising technology to provide environmentally friendly energy vectors. Among the current library of developed photocatalysts, organic conjugated polymers present unique advantages of sufficient light-absorption efficiency, excellent stability, tunable electronic properties, and economic applicability. As a class of rising photocatalysts, organic conjugated polymers offer high flexibility in tuning the framework of the backbone and porosity to fulfill the requirements for photocatalytic applications. In the past decade, significant progress has been made in visible-light-driven water splitting employing organic conjugated polymers. The recent development of the structural design principles of organic conjugated polymers (including linear, crosslinked, and supramolecular self-assembled polymers) toward efficient photocatalytic hydrogen evolution, oxygen evolution, and overall water splitting is described, thus providing a comprehensive reference for the field. Finally, current challenges and perspectives are also discussed.     

Membranes set to play important role in hydrogen economy: Edited by Simon Atkinson

This brief feature identifies the important role that membranes may play in a so-called hydrogen economy by considering recent developments in technologies that are being used to generate and store hydrogen.In such an economy, hydrogen — the most abundant element in the universe — replaces fossil fuels as the primary source of energy.A shift to a hydrogen economy will have widespread benefits to society by reducing environmental pollution and global climate change, as well as greatly reducing our dependence on sources of non-renewable energy.Furthermore, if hydrogen fuel cells are ever to replace petrol engines in cars, they will need a cheap source of highly pure hydrogen.     

Hydrogen from renewable palm kernel shell via enhanced gasification with low carbon dioxide emission

Hydrogen economy has become more attractive with the energy crises and environmental issues associated with fossil fuel utilization more so with the discovery that hydrogen can be produced from renewable biomass. This provides good prospects to Malaysia that generates abundant palm wastes. Nevertheless, there is still limited knowledge on kinetics parameters for hydrogen production from palm kernel shell (PKS) gasification. Hence, this work aims to develop a mathematical model that is able to describe the kinetics of steam gasification of PKS with in situ CO₂ capture while considering tar formation. A mean-squared error minimization approach has been used to estimate the kinetics parameters of the gasification process. Using the calculated kinetics parameters the process efficiencies are profiled with respect to the effect of gasification temperature, steam/biomass ratio and sorbent/biomass ratio. The parametric study indicates that the three variables promote hydrogen production at different degree of influence. This developed model can be further extended to incorporate optimization study on the potential clean production of hydrogen from PKS.     

Carbon‐Rich Nanomaterials: Fascinating Hydrogen and Oxygen Electrocatalysts

Hydrogen energy is commonly considered as a clean and sustainable alternative to the traditional fossil fuels. Toward universal utilization of hydrogen energy, developing high‐efficiency, low‐cost, and sustainable energy conversion technologies, especially water‐splitting electrolyzers and fuel cells, is of paramount significance. In order to enhance the energy conversion efficiency of the water‐splitting electrolyzers and fuel cells, earth‐abundant and stable electrocatalysts are essential for accelerating the sluggish kinetics of hydrogen and oxygen reactions. In the past decade, carbon‐rich nanomaterials have emerged as a promising class of hydrogen and oxygen electrocatalysts. Here, the development and electrocatalytic activity of various carbon‐rich materials, including metal‐free carbon, conjugated porous polymers, graphdiyne, covalent organic frameworks (COFs), atomic‐metal‐doped carbon, as well as metal–organic frameworks (MOFs), are demonstrated. In particular, the correlations between their porous nanostructures/electronic structures of active centers and electrocatalytic performances are emphatically discussed. Therefore, this review article guides the rational design and synthesis of high‐performance, metal‐free, and noble‐metal‐free carbon‐rich electrocatalysts and eventually advances the rapid development of water‐splitting electrolyzers and fuel cells toward practical applications.     

Regulating Water‐Reduction Kinetics in Cobalt Phosphide for Enhancing HER Catalytic Activity in Alkaline Solution

Electrochemical water splitting to produce hydrogen renders a promising pathway for renewable energy storage. Considering limited electrocatalysts have good oxygen‐evolution reaction (OER) catalytic activity in acid solution while numerous economical materials show excellent OER catalytic performance in alkaline solution, developing new strategies that enhance the alkaline hydrogen‐evolution reaction (HER) catalytic activity of cost‐effective catalysts is highly desirable for achieving highly efficient overall water splitting. Herein, it is demonstrated that synergistic regulation of water dissociation and optimization of hydrogen adsorption free energy on electrocatalysts can significantly promote alkaline HER catalysis. Using oxygen‐incorporated Co₂P as an example, the synergistic effect brings about 15‐fold enhancement of alkaline HER activity. Theory calculations confirm that the water dissociation free energy of Co₂P decreases significantly after oxygen incorporation, and the hydrogen adsorption free energy can also be optimized simultaneously. The finding suggests the powerful effectiveness of synergetic regulation of water dissociation and optimization of hydrogen adsorption free energy on electrocatalysts for alkaline HER catalysis.     

A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction

High gravimetric energy density, earth-abundance, and environmental friendliness of hydrogen sources have inspired the utilization of hydrogen fuel as a clean alternative to fossil fuels. Hydrogen evolution reaction (HER), a half reaction of water splitting, is crucial to the low-cost production of pure H₂ fuels but necessitates the use of electrocatalysts to expedite reaction kinetics. Owing to the availability of low-cost oxygen evolution reaction (OER) catalysts for the counter electrode in alkaline media and the lack of low-cost OER catalysts in acidic media, researchers have focused on developing HER catalysts in alkaline media with high activity and stability. Nickel is well-known as an HER catalyst and continuous efforts have been undertaken to improve Ni-based catalysts as alkaline electrolyzers. In this review, we summarize earlier studies of HER activity and mechanism on Ni surfaces, along with recent progress in the optimization of the Ni-based catalysts using various modern techniques. Recently developed Ni-based HER catalysts are categorized according to their chemical nature, and the advantages as well as limitations of each category are discussed. Among all Ni-based catalysts, Ni-based alloys and Ni-based hetero-structure exhibit the most promising electrocatalytic activity and stability owing to the fine-tuning of their surface adsorption properties via a synergistic nearby element or domain. Finally, selected applications of the developed Ni-based HER catalysts are highlighted, such as water splitting, the chloralkali process, and microbial electrolysis cell.

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Techno-economic analysis of organosolv pretreatment process from lignocellulosic biomass

Lignocellulosic ethanol is a promising alternative to replace liquid fossil fuels for the transportation sector in the near future. Organosolv pretreatment has been tested as a method for separating lignin from the biomass and commercializing it as a biopolymer. Based on published laboratory scale data, we propose a feasible process flowsheet for organosolv pretreatment. Simulation of the pretreatment process provided mass and energy balances for a techno-economic analysis, and the values were compared with the most prevalent and mature pretreatment method: diluted acid. Organosolv pretreatment required more energy, 578.1 versus 213.8 MW for diluted acid pretreatment, but resulted in a higher ethanol concentration after the biomass fermentation, 11.1% compared to 5.4%. Total annual costs (TACs) calculations showed advantages for diluted acid pretreatment, but future improvements explored in the sensitivity analysis turned into possible savings of 42.8% in the minimum ethanol selling price for organosolv pretreatment.     

Spatial optimization of biomass power plant site using fuzzy analytic network process

Electricity has a significant role in the sustainable development of societies. Traditional methods of generating electricity face several challenges. The ever-increasing demand for electricity generation on the one hand, and the lack of adequate resources for fossil fuels on the other, has led to the use of renewable energy. Biomass is a renewable energy supply that can be used in electricity generation for a sustainable environment. This study aims to introduce a multi-criteria decision-making framework which integrates a geographical information system with a fuzzy analytic network process together with weighted linear combination to optimize the location of a biomass power plant in Guilan Province, Iran. For this purpose, the environmental and socioeconomic factors were identified, and the main contributing criteria were selected. The results showed that about 27.73 and 41.06% of the region has high or moderate suitability, respectively, for constructing a biomass power plant. In addition, a sensitivity analysis was performed to investigate the robustness of the outcomes of decision making by changing the weighting of the criteria. Results indicated that the ranking of alternative locations is independent of the weights chosen.     

Air-stable magnesium nanocomposites provide rapid and high-capacity hydrogen storage without using heavy-metal catalysts

Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg(-1); ref. 1), great variety of potential sources (for example water, biomass, organic matter), light weight, and low environmental impact (water is the sole combustion product). However, there remains a challenge to produce a material capable of simultaneously optimizing two conflicting criteria--absorbing hydrogen strongly enough to form a stable thermodynamic state, but weakly enough to release it on-demand with a small temperature rise. Many materials under development, including metal-organic frameworks, nanoporous polymers, and other carbon-based materials, physisorb only a small amount of hydrogen (typically 1-2 wt%) at room temperature. Metal hydrides were traditionally thought to be unsuitable materials because of their high bond formation enthalpies (for example MgH(2) has a ΔHf~75 kJ mol(-1)), thus requiring unacceptably high release temperatures resulting in low energy efficiency. However, recent theoretical calculations and metal-catalysed thin-film studies have shown that microstructuring of these materials can enhance the kinetics by decreasing diffusion path lengths for hydrogen and decreasing the required thickness of the poorly permeable hydride layer that forms during absorption. Here, we report the synthesis of an air-stable composite material that consists of metallic Mg nanocrystals (NCs) in a gas-barrier polymer matrix that enables both the storage of a high density of hydrogen (up to 6 wt% of Mg, 4 wt% for the composite) and rapid kinetics (loading in <30 min at 200 °C). Moreover, nanostructuring of the Mg provides rapid storage kinetics without using expensive heavy-metal catalysts.     

The pace and practicality of decarbonization

There is a widely believed myth that replacing the use of fossil fuels largely by renewable forms of energy is, with a possible exception of nuclear power, critically dependent on the development of appropriate new technologies. Accordingly, it is held that decarbonizing straight away is particularly difficult and expensive. There was a time when this idea had an element of reality, but this is no longer the case. Unfortunately, belief in this myth is shared by those in positions of influence. This paper serves to document that this presumed reality no longer holds, although the misconception may have been based on fact in the past. Whilst the survey of the available technology offered concentrates on electricity supply, it also documents that manufacture of synthetic fuels via hydrogen obtained by electrolysis of water and CO₂ integrates smoothly with electricity grid stabilization as well as reducing the CO₂ content of the atmosphere. The likely price and cost development in the energy market is also reviewed. In addition the role of CCS, in practice mainly capture from the air and industrial processes other than power generation is reviewed against the background of the cost effective generation of electricity by harvesting renewable forms of energy.