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.     

Cr‐Doped FeNi–P Nanoparticles Encapsulated into N‐Doped Carbon Nanotube as a Robust Bifunctional Catalyst for Efficient Overall Water Splitting

Exploring high‐efficiency, stable, and cost‐effective bifunctional electrocatalysts for overall water splitting is greatly desirable and challenging. Herein, a newly designed hybrid catalyst with Cr‐doped FeNi–P nanoparticles encapsulated into N‐doped carbon nanotubes (Cr‐doped FeNi–P/NCN) with unprecedented electrocatalytic activity is developed by a simple one‐step heating treatment. The as‐synthesized Cr‐doped FeNi–P/NCN with moderate Cr doping exhibits admirable oxygen evolution reaction and hydrogen evolution reaction activities with overpotentials of 240 and 190 mV to reach a current density of 10 mA cm^?2 in 1 m KOH solution. When used in overall water splitting as a bifunctional catalyst, it needs only 1.50 V to give a current density of 10 mA cm^?2, which is superior to its typically integrated Pt/C and RuO₂ counterparts (1.54 V @ 10 mA cm^?2). Density functional theory calculation confirms that Cr doping into a FeNi‐host can effectively alter the relative Gibbs adsorption energy and reduces the theoretical overpotential. Additionally, the synergetic effects between Cr‐doped FeNi–P nanoparticles and NCNs are regarded as significant contributors to accelerate charge transfer and promote electrocatalytic activity in hybrid catalysts.     

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.     

Tantalum (Oxy)Nitride: Narrow Bandgap Photocatalysts for Solar Hydrogen Generation

Photocatalytic water splitting, which directly converts solar energy into hydrogen, is one of the most desirable solar-energy-conversion approaches. The ultimate target of photocatalysis is to explore efficient and stable photocatalysts for solar water splitting. Tantalum (oxy)nitride-based materials are a class of the most promising photocatalysts for solar water splitting because of their narrow bandgaps and sufficient band energy potentials for water splitting. Tantalum (oxy)nitride-based photocatalysts have experienced intensive exploration, and encouraging progress has been achieved over the past years. However, the solar-to-hydrogen (STH) conversion efficiency is still very far from its theoretical value. The question of how to better design these materials in order to further improve their water-splitting capability is of interest and importance. This review summarizes the development of tantalum (oxy)nitride-based photocatalysts for solar water spitting. Special interest is paid to important strategies for improving photocatalytic water-splitting efficiency. This paper also proposes future trends to explore in the research area of tantalum-based narrow bandgap photocatalysts for solar water splitting.     

Accelerated Hydrogen Evolution Kinetics on NiFe‐Layered Double Hydroxide Electrocatalysts by Tailoring Water Dissociation Active Sites

Owing to its earth abundance, low kinetic overpotential, and superior stability, NiFe‐layered double hydroxide (NiFe‐LDH) has emerged as a promising electrocatalyst for catalyzing water splitting, especially oxygen evolution reaction (OER), in alkaline solutions. Unfortunately, as a result of extremely sluggish water dissociation kinetics (Volmer step), hydrogen evolution reaction (HER) activity of the NiFe‐LDH is rather poor in alkaline environment. Here a novel strategy is demonstrated for substantially accelerating the hydrogen evolution kinetics of the NiFe‐LDH by partially substituting Fe atoms with Ru. In a 1 m KOH solution, the as‐synthesized Ru‐doped NiFe‐LDH nanosheets (NiFeRu‐LDH) exhibit excellent HER performance with an overpotential of 29 mV at 10 mA cm^?2, which is much lower than those of noble metal Pt/C and reported electrocatalysts. Both experimental and theoretical results reveal that the introduction of Ru atoms into NiFe‐LDH can efficiently reduce energy barrier of the Volmer step, eventually accelerating its HER kinetics. Benefitting from its outstanding HER activity and remained excellent OER activity, the NiFeRu‐LDH steadily drives an alkaline electrolyzer with a current density of 10 mA cm^?2 at a cell voltage of 1.52 V, which is much lower than the values for Pt/C–Ir/C couple and state‐of‐the‐art overall water‐splitting electrocatalysts.     

Significant Enhancement of Water Splitting Activity of N‐Carbon Electrocatalyst by Trace Level Co Doping

Replacement of precious metal electrocatalysts with highly active and cost efficient alternatives for complete water splitting at low voltage has attracted a growing attention in recent years. Here, this study reports a carbon‐based composite co‐doped with nitrogen and trace amount of metallic cobalt (1 at%) as a bifunctional electrocatalyst for water splitting at low overpotential and high current density. An excellent electrochemical activity of the newly developed electrocatalyst originates from its graphitic nanostructure and highly active Co‐N_x sites. In the case of carefully optimized sample of this electrocatalyst, 10 mA cm^?2 current density can be achieved for two half reactions in alkaline solutions—hydrogen evolution reaction and oxygen evolution reaction—at low overpotentials of 220 and 350 mV, respectively, which are smaller than those previously reported for nonprecious metal and metal‐free counterparts. Based on the spectroscopic and electrochemical investigations, the newly identified Co‐N_x sites in the carbon framework are responsible for high electrocatalytic activity of the Co,N‐doped carbon. This study indicates that a trace level of the introduced Co into N‐doped carbon can significantly enhance its electrocatalytic activity toward water splitting.     

Metal oxide composites and structures for ultra-high temperature solar thermochemical cycles

Conceptually, thermochemical cycles are heat engines that drive endothermic chemical reactions, e.g., splitting water into hydrogen and oxygen. The two-step metal oxide cycles (typically ferrite-based) are particularly attractive since they are relatively simple, use non-corrosive materials, and involve gas–solid reactions requiring no difficult separations. Additionally, they are potentially the most efficient renewable-energy driven processes for hydrogen production. We are developing a novel concentrating solar power (CSP) driven metal-oxide-based heat engine, the CR5, at the heart of which are rings of a reactive solid that are thermally and chemically cycled to produce oxygen and hydrogen from water in separate and isolated steps. The monolithic ring structures must have high geometric surface area for gas–solid contact and for adsorption of incident solar radiation, and must maintain structural integrity and high reactivity after extensive thermal cycling to temperatures of at least 1,400 °C. We have demonstrated through laboratory and on-sun testing that cobalt ferrite/zirconia mixtures fabricated into monolithic structures suitable for the CR5 are mechanically robust and maintain productivity over tens of cycles. We have also demonstrated that carbon dioxide splitting (CDS) to carbon monoxide and oxygen is a thermodynamically favorable alternative to water splitting that can be conducted with both iron- and cerium-based materials.     

Porous Cobalt Phosphide Polyhedrons with Iron Doping as an Efficient Bifunctional Electrocatalyst

Iron (Fe)‐doped porous cobalt phosphide polyhedrons are designed and synthesized as an efficient bifunctional electrocatalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The synthesis strategy involves one‐step route for doping foreign metallic element and forming porous cobalt phosphide polyhedrons. With varying doping levels of Fe, the optimized Fe‐doped porous cobalt phosphide polyhedron exhibits significantly enhanced HER and OER performances, including low onset overpotentials, large current densities, as well as small Tafel slopes and good electrochemical stability during HER and OER.     

Economizing Production of Diverse 2D Layered Metal Hydroxides for Efficient Overall Water Splitting

2D layered metal hydroxides (LMH) are promising materials for electrochemical energy conversion and storage. Compared with exfoliation of bulk layered materials, wet chemistry synthesis of 2D LMH materials under mild conditions still remains a big challenge. Here, an “MgO‐mediated strategy” for mass production of various 2D LMH nanosheets is presented by hydrolyzing MgO in metal salt aqueous solutions at room temperature. Benefiting from this economical and scalable strategy, ultrathin LMH nanosheets (M = Ni, Fe, Co, NiFe, and NiCo) and their derivatives (e.g., metal oxides and sulfides) can be synthesized in high yields. More importantly, this strategy opens up opportunities to fabricate hierarchically structured LMH nanosheets, resulting in high‐performance electrocatalysts for the oxygen‐ and hydrogen‐evolution reactions to realize stable overall water splitting with a low cell voltage of 1.55 V at 10 mA cm⁻². This work provides a powerful platform for the synthesis and applications of 2D materials.     

Recent progress in oxynitride photocatalysts for visible-light-driven water splitting

Abstract

Photocatalytic water splitting into hydrogen and oxygen is a method to directly convert light energy into storable chemical energy, and has received considerable attention for use in large-scale solar energy utilization. Particulate semiconductors are generally used as photocatalysts, and semiconductor properties such as bandgap, band positions, and photocarrier mobility can heavily impact photocatalytic performance. The design of active photocatalysts has been performed with the consideration of such semiconductor properties. Photocatalysts have a catalytic aspect in addition to a semiconductor one. The ability to control surface redox reactions in order to efficiently produce targeted reactants is also important for photocatalysts. Over the past few decades, various photocatalysts for water splitting have been developed, and a recent main concern has been the development of visible-light sensitive photocatalysts for water splitting. This review introduces the study of water-splitting photocatalysts, with a focus on recent progress in visible-light induced overall water splitting on oxynitride photocatalysts. Various strategies for designing efficient photocatalysts for water splitting are also discussed herein.     

Metal-organic framework derived CoSe2 nanoparticles anchored on carbon fibers as bifunctional electrocatalysts for efficient overall water splitting

The development of efficient,low-cost,stable,non-noble-metal electrocatalysts for water splitting,particularly those that can catalyze both the hydrogen evolution reaction (HER) at the cathode and oxygen evolution reaction (OER) at the anode,is a challenge.We have developed a facile method for synthesizing CoSe2 nanoparticles uniformly anchored on carbon fiber paper (CoSe2/CF) via pyrolysis and selenization of in situ grown zeolitic imidazolate framework-67 (ZIF-67).CoSe2/CF shows high and stable catalytic activity in both the HER and OER in alkaline solution.At a low cell potential,i.e.,1.63 V,a water electrolyzer equipped with two CoSe2/CF electrodes gave a water-splitting current of 10 mA.cm-2.At a current of 20 mA.cm-2,it can operate without degradation for 30 h.This study not only offers a cost-effective solution for water splitting but also provides a new strategy for developing various catalytic nanostructures by changing the metal-organic framework precursors.     

Ultrathin Ni(0)-Embedded Ni(OH)2 Heterostructured Nanosheets with Enhanced Electrochemical Overall Water Splitting

The efficiency of splitting water into hydrogen and oxygen is highly dependent on the catalyst used. Herein, ultrathin Ni(0)-embedded Ni(OH)₂ heterostructured nanosheets, referred to as Ni/Ni(OH)₂ nanosheets, with superior water splitting activity are synthesized by a partial reduction strategy. This synthetic strategy confers the heterostructured Ni/Ni(OH)₂ nanosheets with abundant Ni(0)-Ni(II) active interfaces for hydrogen evolution reaction (HER) and Ni(II) defects as transitional active sites for oxygen evolution reaction (OER). The obtained Ni/Ni(OH)₂ nanosheets exhibit noble metal-like electrocatalytic activities toward overall water splitting in alkaline condition, to offer 10 mA cm⁻² in HER and OER, the required overpotentials are only 77 and 270 mV, respectively. Based on such an outstanding activity, a water splitting electrolysis cell using the Ni/Ni(OH)₂ nanosheets as the cathode and anode electrocatalysts has been successfully built. When the output voltage of the electrolytic cell is 1.59 V, a current density of 10 mA cm⁻² can be obtained. Moreover, the durability of Ni/Ni(OH)₂ nanosheets in the alkaline electrolyte is much better than that of noble metals. No obvious performance decay is observed after 20 h of catalysis. This facile strategy paves the way for designing highly active non-precious-metal catalyst to generate both hydrogen and oxygen by electrolyzing water at room temperature.     

Ruthenium Nanoparticles on Cobalt‐Doped 1T′ Phase MoS2 Nanosheets for Overall Water Splitting

2D MoS₂ nanostructures have recently attracted considerable attention because of their outstanding electrocatalytic properties. The synthesis of unique Co–Ru–MoS₂ hybrid nanosheets with excellent catalytic activity toward overall water splitting in alkaline solution is reported. 1T′ phase MoS₂ nanosheets are doped homogeneously with Co atoms and decorated with Ru nanoparticles. The catalytic performance of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is characterized by low overpotentials of 52 and 308 mV at 10 mA cm^?2 and Tafel slopes of 55 and 50 mV decade^?1 in 1.0 m KOH, respectively. Analysis of X‐ray photoelectron and absorption spectra of the catalysts show that the MoS₂ well retained its metallic 1T′ phase, which guarantees good electrical conductivity during the reaction. The Gibbs free energy calculation for the reaction pathway in alkaline electrolyte confirms that the Ru nanoparticles on the Co‐doped MoS₂ greatly enhance the HER activity. Water adsorption and dissociation take place favorably on the Ru, and the doped Co further catalyzes HER by making the reaction intermediates more favorable. The high OER performance is attributed to the catalytically active RuO₂ nanoparticles that are produced via oxidation of Ru nanoparticles.     

基于多相硫化镍铁的高效析氧电极材料（英文）

开发高效和低成本的析氧电极材料是工业电解水制氢技术发展道路上至关重要的技术难题.本文利用溶剂热方法将镍铁水滑石阵列转化为具有铁掺杂的多相硫化镍(NiS和Ni3S2)阵列,制备出一种具有高效析氧性能的电极材料.粗糙的纳米片表面有利于高活性位点的暴露.电化学分析表明其仅需要100 mV的过电位就可以达到10 mA cm^-2的电流密度,相对于镍铁水滑石阵列降低了130 mV.我们进一步通过密度泛函理论计算来揭示其活性提升机理,发现具有部分S氧化的Fe掺杂NiS可以极大地降低析氧反应中间体形成的阻力,从而加快催化反应进行,提高催化活性.另一方面,(Ni,Fe)S和(Ni,Fe)3S2与三维多孔泡沫镍结构有很好的结合作用,反应电子可以通过金属性的二硫化镍相进行高效传输,进一步加速析氧催化进程.     

Recent progress in oxynitride photocatalysts for visible-light-driven water splitting

Photocatalytic water splitting into hydrogen and oxygen is a method to directly convert light energy into storable chemical energy, and has received considerable attention for use in large-scale solar energy utilization. Particulate semiconductors are generally used as photocatalysts, and semiconductor properties such as bandgap, band positions, and photocarrier mobility can heavily impact photocatalytic performance. The design of active photocatalysts has been performed with the consideration of such semiconductor properties. Photocatalysts have a catalytic aspect in addition to a semiconductor one. The ability to control surface redox reactions in order to efficiently produce targeted reactants is also important for photocatalysts. Over the past few decades, various photocatalysts for water splitting have been developed, and a recent main concern has been the development of visible-light sensitive photocatalysts for water splitting. This review introduces the study of water-splitting photocatalysts, with a focus on recent progress in visible-light induced overall water splitting on oxynitride photocatalysts. Various strategies for designing efficient photocatalysts for water splitting are also discussed herein.     

Novel MOF‐Derived Co@N‐C Bifunctional Catalysts for Highly Efficient Zn–Air Batteries and Water Splitting

Metal–organic frameworks (MOFs) and MOF‐derived materials have recently attracted considerable interest as alternatives to noble‐metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N‐C materials (C‐MOF‐C2‐T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C‐MOF‐C2‐900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N‐doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO₂, respectively. Primary Zn–air batteries based on C‐MOF‐900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h g_Zn^–1 under 10 mA cm^–2. Rechargeable Zn–air batteries based on C‐MOF‐C2‐900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm^–2), along with an excellent cycling stability with no increase in polarization even after 120 h – outperform their counterparts based on noble‐metal‐based air electrodes. The resultant rechargeable Zn–air batteries are used to efficiently power electrochemical water‐splitting systems, demonstrating promising potential as integrated green energy systems for practical applications.     

Strong Electronic Interaction in Dual‐Cation‐Incorporated NiSe2 Nanosheets with Lattice Distortion for Highly Efficient Overall Water Splitting

Exploring highly efficient and low‐cost electrocatalysts for electrochemical water splitting is of importance for the conversion of intermediate energy. Herein, the synthesis of dual‐cation (Fe, Co)‐incorporated NiSe₂ nanosheets (Fe, Co‐NiSe₂) and systematical investigation of their electrocatalytic performance for water splitting as a function of the composition are reported. The dual‐cation incorporation can distort the lattice and induce stronger electronic interaction, leading to increased active site exposure and optimized adsorption energy of reaction intermediates compared to single‐cation‐doped or pure NiSe₂. As a result, the obtained Fe_0.09Co_0.13‐NiSe₂ porous nanosheet electrode shows an optimized catalytic activity with a low overpotential of 251 mV for oxygen evolution reaction and 92 mV for hydrogen evolution reaction (both at 10 mA cm^?2 in 1 m KOH). When used as bifunctional electrodes for overall water splitting, the current density of 10 mA cm^?2 is achieved at a low cell voltage of 1.52 V. This work highlights the importance of dual‐cation doping in enhancing the electrocatalyst performance of transition metal dichalcogenides.     

NiMoFe and NiMoFeP as Complementary Electrocatalysts for Efficient Overall Water Splitting and Their Application in PV‐Electrolysis with STH 12.3%

Complementary water splitting electrocatalysts used simultaneously in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can simplify water splitting systems. Herein, earth‐abundant NiMoFe (NMF) and phosphorized NiMoFeP (NMFP) are synthesized as complementary overall water splitting (OWS) catalysts. First, NMF is tested as both the HER and OER promoter, which exhibits low overpotentials of 68 (HER) and 337 mV (OER). A quaternary NMFP is then prepared by simple phosphorization of NMF, which shows a much lower OER overpotential of 286 mV. The enhanced OER activity is attributed to the unique surface/core structure of NMFP. The surface phosphate acts as a proton transport mediator and expedites the rate‐determining step. With the application of OER potential, the NMFP surface is composed of Ni(OH)₂ and FeOOH, active sites for OER, but the inner core consists of Ni, Mo, and Fe metals, serving as a conductive electron pathway. OWS with NMF‐NMFP requires an applied voltage of 1.452 V to generate 10 mA cm^?2, which is one of the lowest values among OWS results with transition‐metal‐based electrocatalysts. Furthermore, the catalysts are combined with tandem perovskite solar cells for photovoltaic (PV)‐electrolysis, producing a high solar‐to‐hydrogen (STH) conversion efficiency of 12.3%.     

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。     

Amorphous Catalysts and Electrochemical Water Splitting: An Untold Story of Harmony

In the near future, sustainable energy conversion and storage will largely depend on the electrochemical splitting of water into hydrogen and oxygen. Perceiving this, countless research works focussing on the fundamentals of electrocatalysis of water splitting and on performance improvements are being reported everyday around the globe. Electrocatalysts of high activity, selectivity, and stability are anticipated as they directly determine energy‐ and cost efficiency of water electrolyzers. Amorphous electrocatalysts with several advantages over crystalline counterparts are found to perform better in electrocatalytic water splitting. There are plenty of studies witnessing performance enhancements in electrocatalysis of water splitting while employing amorphous materials as catalysts. The harmony between the flexibility of amorphous electrocatalysts and electrocatalysis of water splitting (both the oxygen evolution reaction [OER] and the hydrogen evolution reaction [HER]) is one of the untold and unsummarized stories in the field of electrocatalytic water splitting. This Review is devoted to comprehensively discussing the upsurge of amorphous electrocatalysts in electrochemical water splitting. In addition to that, the basics of electrocatalysis of water splitting are also elaborately introduced and the characteristics of a good electrocatalyst for OER and HER are discussed.