Recent development in electrocatalysts for hydrogen production through water electrolysis

Hydrogen is a carbon-free alternative energy source for use in future energy frameworks with the advantages of environment-friendliness and high energy density. Among the numerous hydrogen production techniques, sustainable and high purity of hydrogen can be achieved by water electrolysis. Therefore, developing electrocatalysts for water electrolysis is an emerging field with great importance to the scientific community. On one hand, precious metals are typically used to study the two-half cell reactions, i.e., hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, precious metals (i.e., Pt, Au, Ru, Ag, etc.) as electrocatalysts are expensive and with low availability, which inhibits their practical application. Non-precious metal-based electrocatalysts on the other hand are abundant with low-cost and eco-friendliness and exhibit high electrical conductivity and electrocatalytic performance equivalent to those for noble metals. Thus, these electrocatalysts can replace precious materials in the water electrolysis process. However, considerable research effort must be devoted to the development of these cost-effective and efficient non-precious electrocatalysts. In this review article, we provide key fundamental knowledge of water electrolysis, progress, and challenges of the development of most-studied electrocatalysts in the most desirable electrolytic solutions: alkaline water electrolysis (AWE), solid-oxide electrolysis (SOE), and proton exchange membrane electrolysis (PEME). Lastly, we discuss remaining grand challenges, prospect, and future work with key recommendations that must be done prior to the full commercialization of water electrolysis systems.     

Novel alkaline water electrolysis with nickel-iron gas diffusion electrode for oxygen evolution

In the present work, a novel electrolyzer concept for alkaline water electrolysis (AEL) with a gas diffusion electrode (GDE) as anode, a conventional immersed porous cathode and a state-of-the-art Zirfon™ separator is presented and compared with a conventional electrolyzer setup. Due to the utilization of a GDE in this configuration, the electrolyte is only circulated through the cathode compartment which greatly simplifies the process. The influence of the catalyst composition and the enhanced electrode surface owing to the three-dimensional porous structure of the GDE are characterized and investigated regarding the electrode performance. Furthermore, process parameters like contact pressure and differential pressure are examined and optimized. The novel process concept with a GDE as anode reveals a similar cell potential compared to a classical electrolysis cell with a Ni/Fe-coated nickel foam anode up to 400 mA cm⁻² at 353 K and 32.5 wt% KOH and also exhibits relatively good electrochemical stability over time.     

Laser structured nickel-iron electrodes for oxygen evolution in alkaline water electrolysis

In the present work, the ultra-short pulse laser ablation method is applied to create novel surface alloys on NiFe electrodes for the oxygen evolution reaction (OER) in alkaline water electrolysis. The nickel-to-iron ratio in the alloy can be controlled with the ultra-short pulse laser ablation method by varying the thickness of electrochemically deposited iron layers onto the nickel mesh substrate. Besides the application of the additional catalyst, the laser treatment enhances the surface area and a defined micro- and submicrometer structure is created in a single step. The laser structured nickel-iron electrodes show a significantly lower overpotential of 249 mV than an electrochemically deposited Ni-NiFe alloy with 292 mV at 10 mA cm⁻², 298 K and 32.5 wt% KOH for the OER, although some loss of iron over time could not be prevented.     

Co/Mo2C composites for efficient hydrogen and oxygen evolution reaction

Non-precious transition metal electrocatalysts with high catalytic performance and low cost enable the scalable and sustainable production of hydrogen energy through water splitting. In this work, based on the polymerization of CoMoO₄ nanorods and pyrrole monomer, a heterointerface of carbon-wrapped and Co/Mo₂C composites are obtained by thermal pyrolysis method. Co/Mo₂C composites show considerable performance for both hydrogen and oxygen evolution in alkaline media. In alkaline media, Co/Mo₂C composites show a small overpotential, low Tafel slope, and excellent stability for water splitting. Co/Mo₂C exhibits a small overpotential of 157 mV for hydrogen evolution reaction and 366 mV for oxygen evolution reaction at current density of 10 mA cm⁻², as well as a low Tafel slope of 109.2 mV dec⁻¹ and 59.1 mV dec⁻¹ for hydrogen evolution reaction and oxygen evolution reaction, respectively. Co/Mo₂C composites also exhibit an excellent stability, retaining 94% and 93% of initial current value for hydrogen evolution reaction and oxygen evolution reaction after 45,000 s, respectively. Overall water splitting via two-electrode water indicates Co/Mo₂C can hold 91% of its initial current after 40,000 s in 1 M KOH.     

CoP@NC electrocatalyst promotes hydrogen and oxygen productions for overall water splitting in alkaline media

Design and synthesis of high-performance bi-functional electrocatalysts can play a crucial role for electrolytic water splitting. Herein, we develop a simple phosphating process to construct cobalt phosphide@nitrogen-doped carbon (CoP@NC) using metal organic frame (MOF) as a precursor and a template. In alkaline solution, CoP@NC-350 exhibits exceptional hydrogen and oxygen evolution reaction performances with over potentials of 75 mV and 268 mV at 10 mA cm^?2, respectively. For a symmetric CoP@NC-350 two-electrode water splitting setup, the potential can be low as 1.69 V to obtain 10 mA cm^?2. Therefore, low-temperature phosphating treatment can be a simple and promising method to produce electrocatalysts for water splitting.     

碱性水电解非贵金属析氧催化剂的研究进展

"绿氢"能源的大规模应用依赖于电解水技术。和析氢反应(HER)相比,析氧反应(OER)是水电解过程中的关键反应,其动力学反应缓慢。目前,非贵金属OER电催化剂的活性和稳定性不佳,深入OER过程机理的理解和催化剂活性方面的研究有助于OER速率的提升。文章综述了近年来在碱性体系中对水电解制氢非贵金属析氧催化剂的研究讨论、分析和总结,主要从材料掺杂类、形貌调控类、调节电子结构类和复合结构类4个方面来阐述。     

Structure optimization and electronic modulation of sulfur-incorporated cobalt nanocages for enhanced oxygen evolution

Cobalt-based oxides and hydroxides have always been one of the optimal catalysts for Oxygen Evolution Reaction (OER) in alkaline environment in recent years. However, it remains a challenge for simple cobalt oxides such as CoO, Co₃O₄ and CoOOH to provide high catalytic activity both with ideal conductivity and stability. Herein, we prepared a new type of sulfur-incorporated cobalt oxide nanocages as high efficiency OER catalyst using Co-MOF as precursor. With the help of sodium sulfide, one step water-warm immersion-alcohol refluxing method can achieve the cavitation of precursors and uniform incorporation of sulfur atoms meanwhile. The hollow cubic structure constructed by fluffy nanosheets is beneficial to the exposure of active sites, the regulation of electronic structure and improve the electron transfer speed. After electrochemical testing, the prepared CoS@CoO showed outstanding OER activity compared with other cobalt-based catalysts. More importantly, this material has also withstood the electrochemical test of long range due to the stable structural foundation provided by Co-MOF. This work comes up with a new idea for OER activity promotion of hollow doped cobalt-based catalysts through morphology control and electronic structure optimization.     

Development and operation of alternative oxygen electrode materials for hydrogen production by high temperature steam electrolysis

High temperature steam electrolysis (HTSE) is one of the most promising ways for hydrogen mass production. To make this technology suitable from an economical point of view, each component of the system has to be optimized, from the balance of plant to the single solid oxide electrolysis cell. At this level, the optimization of the oxygen electrode is of particular interest since it contributes to a large extent to the cell polarization resistance. The present paper is focused on alternative oxygen electrode materials with improved performances compared to the usual ones mainly based on perovskite structure. Two nickelates, with compositions La₂NiO_4+δ and Nd₂NiO_4+δ are investigated and evaluated in HTSE operation at the button cell level. The performances of the Ln₂NiO_4+δ - containing cells (Ln = La, Nd) is improved compared to a cell containing the classical Sr-doped LaMnO₃ (LSM) perovskite oxygen electrode showing that nickelates are promising candidates for HTSE oxygen electrodes, especially for operation below 800 °C. Indeed, current densities determined at 1.3 V are 1.1 times larger for the La₂NiO_4+δ - containing cell and 1.6 times larger for the Nd₂NiO_4+δ one compared to the LSM - containing cell at 850 °C, whereas at 750 °C they are 1.8 and 4.4 times larger, respectively. Thanks to the use of a reference electrode, by coupling impedance spectroscopy and polarization measurements, the overpotential of each working electrode is deconvoluted from the complete cell voltage under HTSE operating conditions.     

Process kinetics for the electrocatalytic hydrogen evolution reaction on carbon-based Ni/NiO nanocomposite in a single-chamber microbial electrolysis cell

To explore the process kinetics of hydrogen evolution reaction (HER) on carbon-based Ni/NiO nanocomposite in the microbial electrolysis cells (MECs), the performance was systematically studied by different time-course sampling of five parallel single-chamber MECs operated under identical operating conditions, which included the electrochemical performance of anodes and cathodes, and the mechanism and kinetics of HER. It was hypothesized that the decreased performance of the nickel cathodes was due to corrosion and Ni dissolution. These results provide valuable insights into the effects of long-term operation on MEC performance.     

Hydrogen evolution reaction in PTFE bonded Raney-Ni electrodes

This study is concerned with the hydrogen evolution reaction (HER) in several PTFE bonded Raney-Ni electrodes as function of temperature and treatments. The Mo-doped Raney-Ni catalysts are activated by hours of long cathodic polarization interleaved with few deep “charge - discharge” (polarity reversal) cycles. Moreover, the HER efficiency of the electrode requires additives which enhance conductivity and surface properties: with powders of Ni alloys (Ni-Ti, Ni-Cr, Ni-Fe) the electrode becomes also more stable, and almost insensitive to polarity reversal. The main effect of a temperature increase is the reduction of the Tafel slope, which is about 120 mV/dec at 25 °C, and about 60 mV/dec at 60 °C. A proper choice of additives yield electrodes which withstand polarity reversal and may be used in electrolysers which are intermittently operated, or have anodes which require periodic in situ re-activation by reduction.     

Ternary NiCoFe nanosheets for oxygen evolution in anion exchange membrane water electrolysis

Tuning nickel-based catalyst activity and understanding electrolyte and ionomer interaction for oxygen evolution reaction (OER) is crucial to improve anion exchange membrane (AEM) water electrolyzers. Herein, an investigation of multimetallic Ni_0.6Co_0.2Fe_0.2 OER activity, coupled with in-situ Raman spectroscopy to track dynamic structure changes, was carried out and compared to other Ni catalysts. The effect of KOH concentration, KOH purity, ionomer type, and electrolyte with organic cations was evaluated. The Ni_0.6Co_0.2Fe_0.2 catalyst achieved 10 mA/cm² at 260 mV overpotential with stability over 50 h and 5000 cycles in 1 M KOH. In-situ Raman spectroscopy showed that Ni_0.6Co_0.2Fe_0.2 activity originates from promoting Ni(OH)₂/NiOOH transformation at low potentials compared to bi- and mono-metallic nickel-based catalysts. Fumion anion ionomer in the catalyst inks led to a lower OER activity than catalysts with inks containing Nafion ionomer. The OER activity of Ni_0.6Co_0.2Fe_0.2 is adversely influenced in the presence of fumion anion ionomer and benzyltrimethylammonium hydroxide (BTMAOH) with possible phenyl oxidation under applied high anodic potentials. The alkaline AEM water electrolyzer circulating 1 M KOH electrolyte, with a Pt/C cathode and a Ni_0.6Co_0.2Fe_0.2 anode, achieved 1.5 A/cm² at 2 V.     

Iron-doped metal-organic framework with enhanced oxygen evolution reaction activity for overall water splitting

Water electrolysis is an energy conversion technology to provide green and clean hydrogen energy. Developing a high-efficient and durable electrocatalyst is a critical material for water electrolysis. Therefore, we synthesize a series of iron-doped metal-organic frameworks (MOFs) by a facile one-pot hydrothermal method. In the conventional three-electrode-cell, the Co/Fe (1:1)-MOF catalyst exhibits an overpotential of 317 mV at a current density of 10 mA cm⁻² in the oxygen evolution reaction (OER). Furthermore, the electrolysis performance of Co/Fe (1:1)-MOF catalyst is further evaluated in a home-made anion-exchange-membrane water electrolysis cell. With the Co/Fe (1:1)-MOF as the OER catalyst and commercial Pt/C as the hydrogen-evolution-reaction catalyst, the cell presents an overpotential of 490 mV at a large current density of 500 mA cm⁻², which is superior to the benchmark cell with commercial IrO₂ as the OER catalyst in the alkaline media. Theoretical calculation demonstrates that the introduction of Fe dopant into MOFs significantly reduces the binding energy of 1O and 1OOH intermedium during the OER progress. Consequently, the electrocatalytic activity is increased, which is perfectly consistent with the experimental results. This work suggests that the iron-doped MOFs structure significantly improves the electrocatalytic activity and provides a facile strategy to produce hydrogen at a large current density for industrial water electrolysis.     

High-throughput chainmail catalyst FeCo@C nanoparticle for oxygen evolution reaction

Oxygen evolution reaction (OER) is a key part of water electrolysis for hydrogen production. Non-noble-metal catalysts with high activity, stability, but low cost are prerequisites for practical application. In this work, sucrose char was synthesized and then chainmail catalysts were produced by in situ growth method, defined as M@C (M = Fe, Co and FeCo). FeCo@C showed great OER performance in both catalytic activity and durability tests. The overpotentials were 302 mV (at the current density of 10 mA cm⁻²) and 423 mV (at 50 mA cm⁻²), with a lowest Tafel slope of 75 mV dec⁻¹. The electrochemical surface area of catalysts were also analyzed by calculating the capacitance of the double layer to further investigate the catalytic activity. Furthermore, FeCo@C showed superior stability after 30 h test or 10,000 cycles of cyclic voltammetry. Theoretical calculation based on density functional theory (DFT) demonstrated that the overpotential of OER was determined by the Gibbs free energies of reaction intermediates HO1, O1 and HOO1. The adsorption of HO1 radicals onto the FeCo@C was weaker than Fe@C, which was favorable for reducing the overpotential, as the rate-determining step of the OER process over these catalysts was that HO1 dehydrogenated to form O1.     

Metal organic frameworks: Mastery in electroactivity for hydrogen and oxygen evolution reactions

Electrochemical water splitting is recognized as a conspicuous technique for sustainable and an alternative energy storage systems. Fabricating different catalysts for electrocatalysis is highly desirable to decrease the overpotential and ease practical applications. Metal-organic-frameworks (MOFs) have obtained significant consideration recently due to tunable porous structure, superior catalytic activity, and high surface area. Owing to the properties of MOF, these materials can be employed as catalysts for overall water splitting applications. Herein, the most recent advancement in MOFs for an efficient electrochemical water splitting are demonstrated. Primarily, the basics and reaction mechanisms of water splitting were summarized which is followed by the recent improvements in electrocatalytic properties of pristine MOFs, guest@MOFs, MOF derived different metallic compounds and carbon-based catalytic materials. The fast growing innovations in the electrocatalytic activities and their fundamental mechanisms are comprehensively summarized. Finally, a thorough discussion on the current challenges and future outlooks in water splitting is provided.     

Development of efficient membrane electrode assembly for low cost hydrogen production by anion exchange membrane electrolysis

Electrochemical production of hydrogen from water using anion exchange membranes (AEMs) can be achieved with non-noble catalysts, other than traditional proton exchange membranes that use platinum group metals. Using non-noble metals in the catalyst layer will reduce the capital costs associated with water electrolysis systems. The objectives of this study were to develop an effective membrane electrode assembly (MEA) for AEM electrolysis and to determine the effects of various operating parameters on AEM electrolysis. Here, the MEA consisted of the commercially available A-201 AEM and non-noble transition metal oxides as catalysts. The best electrolysis performance recorded was 500 mA cm^?2 for 1.95 V at 60 °C with 1% K₂CO₃ electrolyte. For the purpose of comparison, we also considered commercially available AEMs for AEM electrolysis: Fumapem^® FAA-3 and Fumapem^® FAA-3-PP-75. The performances achieved with these AEMs were comparable with the performance recorded for the conventional AEM A-201. Overall, our results indicated that AEM electrolysis clearly manifests the feasibility of commercial viability.     

Recent advances in cobalt disulfide for electrochemical hydrogen evolution reaction

Hydrogen production by water electrolysis is the most promising green hydrogen supply method in the future. Electrocatalytic hydrogen evolution reaction (HER), an essential step in water electrolysis, has received continuous interest for a long time. Noble metal-based electrocatalysts exhibit excellent performance for HER, while their high price, limited reserves, and insufficient durability limit their large-scale applications. Transition metal sulfides (TMSs) have been extensively studied as potential alternative catalysts, among which cobalt disulfide (CoS₂) stands out due to its unique structure, low price, and good electrical conductivity. Although remarkable progress has been made, the catalytic activity and stability of CoS₂ electrode materials themselves are still insufficient for large-scale industrial applications, so effective improvement of the HER catalytic performance of CoS₂ remains the focus of research. In this review, we briefly outline the reaction mechanism of HER, focusing on strategies to improve the catalytic performance of CoS₂, including morphology engineering, carbon materials combination, heteroatom doping, and heterostructure construction. Furthermore, the key challenges and opportunities for CoS₂ electrode materials as an electrocatalytic material for HER are discussed.     

Electrochemically fabricated NiCu alloy catalysts for hydrogen production in alkaline water electrolysis

NiCu alloy catalysts for alkaline water electrolysis were prepared by an electrodeposition method varying the alloy composition. When the deposition potential became more positive, the bulk and surface Cu content in NiCu alloys as well as the catalyst particle size gradually increased, which were confirmed by various spectroscopic and electrochemical techniques. The surface coverage of the catalysts was found to be a function of the deposition potential, as well. The catalytic activities of the prepared NiCu alloys to hydrogen evolution reaction (HER) were investigated with cyclic voltammetry in a 6.0 M KOH electrolyte at 298 K, and the mass activities of NiCu alloys were correlated with bulk and surface Cu contents to investigate the Cu alloying effect.     

NiCo2O4 nanowire arrays rich in oxygen deficiencies for hydrogen evolution reaction

The rational design of highly efficient electrocatalysts to generate hydrogen by catalyzing hydrogen evolution reaction still remains a challenge. Herein, we report a simple strategy to significantly enhance the catalytic activities of NiCo₂O₄ nanowire arrays by simply tuning the amount of oxygen vacancies. Remarkably, the oxygen-deficient NiCo₂O₄ catalysts obtained in Ar environment show significantly improved catalytic activities toward hydrogen evolution reaction with the requirement of 104 mV overpotential to afford 10 mA cm⁻², 122 mV less than that for air-sintered NiCo₂O₄ (226 mV). Moreover, such catalysts also exhibit superior long-term durability for 24 h at 100 mA cm⁻². The present study further promotes the application of NiCo₂O₄ in other energy storage and conversion system.     

Mesoporous nickel-sulfide/nickel/N-doped carbon as HER and OER bifunctional electrocatalyst for water electrolysis

The development of non-precious metal-based highly active bi-functional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is critical factor for making water electrolysis a viable process for large-scale industrial applications. In this study, bi-functional water splitting electrocatalysts in the form of nickel-sulfide/nickel nanoparticles integrated into a three-dimensional N-doped porous carbon matrix, are prepared using NaCl as a porous structure-forming template. Microstructures of the catalytic materials are characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and N₂ adsorption-desorption analysis. The most active catalyst synthesized in this study exhibits a low HER overpotential of 70 mV at 10 mA cm⁻² and a low Tafel slope of 45 mV dec⁻¹. In OER, the optimized sample performs better than a state-of-the-art RuO₂ catalyst and produces an overpotential of 337 mV at 10 mA cm⁻², lower than that of RuO₂. The newly obtained materials are also used as HER/OER electrocatalysts in a specially assembled two-electrode water splitting cell. The cell demonstrates high activity and good stability in overall water splitting.     

Microwave-assisted facile synthesis of cobaltiron oxide nanocomposites for oxygen production using alkaline anion exchange membrane water electrolysis

In this study, a rapid, scalable, and cost-effective method was developed for synthesizing cobalt–iron metal oxide catalysts for water electrolysis. Cobalt-iron metal oxide catalysts were synthesized using the microwave-assisted hydrothermal methods by varying the molar ratios of cobalt and iron. When the cobalt to iron ratio was 2:1, its electrolytic cell yielded the onset potential of only 1.56 V at 10 mA cm⁻², which is close to the thermodynamically reversible potential. When its cell potential was at 1.8 V, the cell current density was approximately 130 mA cm⁻². The results of the stability test showed a steady-state cell current density of 130 mA cm⁻² and remained constant for more than 16 h at a continuous cell potential of 1.8 V. Compared with other catalysts, cobalt–iron metal oxide catalysts showed lower overpotential and lower Tafel slope than did conventional precious metal catalysts such as PtO₂ and IrO₂. Cobalt-iron metal oxide catalysts serve as an inexpensive route to large-scale commercialization through facile synthesis for enhanced electrochemical water splitting.