Water Electrolysis Research Articles

Material Engineering Strategies for Efficient Hydrogen Evolution Reaction Catalysts.

Water electrolysis, a key enabler of hydrogen energy production, presents significant potential as a strategy for achieving net-zero emissions. However, the widespread deployment of water electrolysis is currently limited by the high-cost and scarce noble metal electrocatalysts in hydrogen evolution reaction (HER). Given this challenge, design and synthesis of cost-effective and high-performance alternative catalysts have become a research focus, which necessitates insightful understandings of HER fundamentals and material engineering strategies. Distinct from typical reviews that concentrate only on the summary of recent catalyst materials, this review article shifts focus to material engineering strategies for developing efficient HER catalysts. In-depth analysis of key material design approaches for HER catalysts, such as doping, vacancy defect creation, phase engineering, and metal-support engineering, are illustrated along with typical research cases. A special emphasis is placed on designing noble metal-free catalysts with a brief discussion on recent advancements in electrocatalytic water-splitting technology. The article also delves into important descriptors, reliable evaluation parameters and characterization techniques, aiming to link the fundamental mechanisms of HER with its catalytic performance. In conclusion, it explores future trends in HER catalysts by integrating theoretical, experimental and industrial perspectives, while acknowledging the challenges that remain.

Efficient Decoupled Electrolytic Water Splitting in Acid through Pseudocapacitive TiO2.

Water electrolysis remains a key component in the societal transition to green energy. Membrane electrolyzers are the state-of-the-art technology for water electrolysis, relying on 80°C operation in highly alkaline electrolytes, which is undesirable for many of the myriad end-use cases for electrolytic water splitting. Herein, an alternative water electrolysis process, decoupled electrolysis, is described which performed in mild acidic conditions with excellent efficiencies. Decoupled electrolysis sequentially performs the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), at the same catalyst. Here, H+ ions generated from the OER are stored through pseudocapacitive (redox) charge storage, and released to drive the HER. Here, decoupled electrolysis is demonstrated using cheap, abundant, TiO2 for the first time. To achieve decoupled acid electrolysis, ultra-small anatase TiO2 particles (4.5nm diameter) are prepared. These ultra-small TiO2 particles supported on a carbon felt electrode show a highly electrochemical surface area with a capacitance of 375Fg-1. When these electrodes are tested for decoupled water splitting an overall energy efficiency of 52.4% is observed, with excellent stability over 3000 cycles of testing. This technology can provide a viable alternative to membrane electrolyzers-eliminating the need for highly alkaline electrolytes and elevated temperatures.

Renewable energy storage using hydrogen produced from seawater membrane-less electrolysis powered by triboelectric nanogenerators

Utilization of widely available seawater for hydrogen generation using robust electrolysis methods can provide sustainable solutions to energy carriers. Sea waves at the same time provide abundant renewable energy that can produce the electricity required for seawater electrolysis. This work presents a novel design for a self-powered hydrogen generation based on membrane-less seawater electrolysis integrated with spring-assisted spherical triboelectric nanogenerators. To streamline fabrication and minimize maintenance expenses, water electrolysis is conducted in a membrane-less electrochemical cell reactor. Employing a mathematical model, the system's performance is analyzed across different catalysts, electrolytes, and operational temperatures. The modeling outcomes indicate that elevating the cell's temperature can lower the necessary potential, enhancing overall electrochemical cell efficiency and decreasing capacitor charging duration. The voltage required for the cell to reach 100 mA cm−2 in the seawater decreases from 2.4 V to 1.9 V as the cell temperature increase from 25 °C to 70 °C. This is due to the decline in the hydrogen and oxygen evolution reaction overpotentials for NPNNS and Ti supported PtPd from 351 mV to 246 mV and 568 mV–394 mV, respectively. Furthermore, increase in the temperature results in an additional 19 % improvement in cell efficiency from 78 % to 97 % and producing hydrogen per cycle during electrolysis of seawater increase from 0.015 μmole to 0.020 μmole.

Analysis of Kinetic and Ohmic Resistances in PEM Water Electrolysis through Reference Electrode Measurements

Analysis of Kinetic and Ohmic Resistances in PEM Water Electrolysis through Reference Electrode Measurements

Performance Evaluation and Durability Analysis of NiFeCoOx Catalysts for Alkaline Water Electrolysis in Anion Exchange Membrane Electrolyzers

Performance Evaluation and Durability Analysis of NiFeCoOx Catalysts for Alkaline Water Electrolysis in Anion Exchange Membrane Electrolyzers

Catalytic activity of Ni–Cr–Fe–Mo porous materials for hydrogen evolution reaction in alkaline media

The hydrogen evolution reaction (HER) based on water electrolysis represents an ideal approach for hydrogen production. The advancement of highly active non-precious metal catalysts holds paramount importance. This research employed powder metallurgy sintering to prepare Ni–Cr–Fe and Ni–Cr–Fe–Mo porous materials. It investigated the impact of Mo doping and sintering temperature on the catalytic activity and microstructural influence of hydrogen evolution materials. Furthermore, the materials' electrochemical performance and long-term stability in 6 mol/L KOH were examined. In complicated systems, the current work provides a feasible method for producing hydrogen from Ni–Cr–Fe–Mo porous materials in a strong alkali environment. The results exhibited that when Mo content is 5% and the sintering temperature is 800 °C, the porosity of Ni–Cr–Fe–Mo porous materials is up to 39.9% and the catalytic activity is up to 97%. At the same time, the current density decays to 7.1% after 1000 cycles of electrolysis and shows good HER stability after 48 h. The enhanced catalytic activity for hydrogen evolution emanated from the positive synergy among the transition metal elements.

Enhancing the physicochemical properties of nickel cobaltite catalyst for oxygen evolution reaction in anion exchange membrane water electrolyzers

Enhancing the physicochemical properties of nickel cobaltite catalyst for oxygen evolution reaction in anion exchange membrane water electrolyzers

From Quinary Co–Cu–Mo–Pd–Re Materials Libraries to Gas Diffusion Electrodes for Alkaline Hydrogen Evolution

AbstractDeveloping a hydrogen evolution reaction (HER) electrocatalyst that can steadily drive a large current density is of great significance for industrial electrochemical water‐splitting technology. Herein, the compositionally complex noble‐metal‐lean system Co–Cu–Mo–Pd–Re is investigated for alkaline HER by a scanning droplet cell‐assisted high‐throughput screening of co‐sputtered thin‐film material libraries. The identified hit compositions are used to prepare a catalyst‐coated Ni foam‐based layer that is hot‐pressed with a specifically designed PEEK‐covered carbon‐based gas diffusion layer to obtain a novel‐design gas diffusion electrode (GDE). H2 bubbles that collect on the electrode surface are effectively reduced by controlling the hydrophobicity of the catalyst layer of the GDE, hence enabling a high current (−1 A cm−2) operation for HER in alkaline water electrolysis.

Mn-doped nickel-copper phosphides as oxygen evolution reaction electrocatalyst in alkaline seawater solution

Compared with traditional water electrolysis, electrolysis of seawater has larger resources and a brighter future. However, seawater contains more elements that have greater corrosive effects on electrodes; especially chloride ions (seawater contains more chloride ions) have the greatest impact. The existence of the corrosion problem creates greater difficulties in electrolyzing seawater, further limiting the efficiency of the electrocatalyst for electrolysis of seawater. In this paper, we report a Mn-doped Ni2P/Cu3P as an environmentally friendly monofunctional electrode for seawater electrolysis, which was made by a simple hydrothermal phosphatization operation method. The experimental results show that Mn-doped Ni2P/Cu3P presents overpotential of only 161 mV for oxygen evolution reaction (OER) at iR compensation of 90 and a current density of 10 mA cm−2. It has a small Tafel slope (25.15 mV dec−1) and a large capacitance (9.58 mF cm−2 on 1 × 1 nickel foam), which exceeds most reported oxygen evolution activities of non-precious metal-based electrocatalysts for electrolysis of alkaline seawater. The performance of Ni2P/Cu3P was probably significantly enhanced due to Mn doping by some characterization means. Through Density functional theory (DFT) analysis, it is known that the doping of Mn gives a large enhancement in the adsorption energy of water when Ni2P/Cu3P is electrolyzed with seawater. This paper provides train of thought for the exploration of excellent electrocatalysts for electrolysis of alkaline seawater.

Evaluating the Fe-doping effect on intermediate adsorption modulation for Co-based vanadates toward separation of hydrogen from water electrolysis

The optimization of intermediate adsorption is pivotal for enhancing the efficacy of catalysts in oxygen evolution reaction (OER). However, many Co-based catalysts exhibit excessive binding energy toward intermediates, thereby restricting the desorption process. To address this issue, we utilized the Co-based vanadates (CoV) as a model and observed that the incorporation of Fe can effectively mitigate the substantial accumulation of intermediates around the catalysts, achieving a balance between the adsorption and desorption. It can be attributed to the Fe-doping, which modulated the electronic structure of CoV, subsequently increasing the catalytic sites and intrinsic activity. As a result, the CoV-Fe exhibited a low overpotential of 260 mV at 20 mA cm−2, which decreased by 82 mV compared to pristine CoV. Besides, the electrolyzer based on CoV-Fe maintained a low cell of 1.46 V for water splitting and held a considerable attenuation of 4.49 % after 200 h of long-term operation.

Attaining Substantially Enhanced Oxygen Evolution Reaction Rates on Ni Foam Catalysts in a Gas Diffusion Electrode Setup

Water electrolysis plays a central role in the transition to a fossil‐free society, but there are significant challenges to overcome in order to increase its availability on a large scale. Alkaline water electrolysis is a mature and scalable technology, although it has several disadvantages compared to electrolyzers working in acidic environments. In particular, the use of highly alkaline aqueous electrolytes can lead to corrosion, and the achieved current densities are relatively low. This study addresses the latter limitation by introducing a gas diffusion electrode (GDE) setup as a novel development tool that bridges the gap between research and practical applications in commercial devices such as fuel cells and electrolyzers. A high surface area Ni foam catalyst that can sustain exceptional oxygen evolution reaction (OER) current densities of up to 4 A cm−2 in a quasi‐steady‐state within our GDE setup operating in an alkaline environment is presented. The high performance of this Ni‐based benchmark catalyst is attributed to its deposition onto a mesh‐like porous transport layer (PTL) via hydrogen‐templated electrodeposition. This forms a porous foam‐like structure that augments the mass transport of the gaseous reactants at the GDE.

Atomically dispersed hexavalent iridium oxide from MnO2 reduction for oxygen evolution catalysis.

Hexavalent iridium (IrVI) oxide is predicted to be more active and stable than any other iridium oxide for the oxygen evolution reaction in acid; however, its experimental realization remains challenging. In this work, we report the synthesis, characterization, and application of atomically dispersed IrVI oxide (IrVI-ado) for proton exchange membrane (PEM) water electrolysis. The IrVI-ado was synthesized by oxidatively substituting the ligands of potassium hexachloroiridate(IV) (K2IrCl6) with manganese oxide (MnO2). The mass-specific activity (1.7 × 105 amperes per gram of iridium) and turnover number (1.5 × 108) exceeded those of benchmark iridium oxides, and in situ x-ray analysis during PEM operations manifested the durability of IrVI at current densities up to 2.3 amperes per square centimeter. The high activity and stability of IrVI-ado showcase its promise as an anode material for PEM electrolysis.

Ultra-High Performance of In Situ Constructed Trimetallic (Pd, Fe, Co) Nanoparticles on Carbon Paper as an Electrocatalyst for Large Current Density Oxygen Evolution Reaction in Alkaline Seawater

Abstract Seawater electrocatalysis holds significant promise as a technology for hydrogen production. A simple and low-cost impregnation-hydrothermal and thermal reduction strategy was used to synthesis in-situ constructed three-dimensional porous trimetallic (Pd, Fe, and Co) anchored on a cheap and high-conducting carbon paper (CP) electrode for water electrolysis in alkaline media. The fabricated PdFeCo1−xONPs@CP electrode had superhydrophilic and superaerophobic properties, allowing for efficient removal of oxygen bubbles from the electrode surface due to the close interaction between the electrode and electrolyte. Furthermore, the synergistic effect of trimetallics and CP-fibers significantly increased OER intrinsic activity. PdFeCo1−xONPs@CP catalyst demonstrated critical low overpotentials of 220 and 300 mV, resulting in an extraordinarily high current density of 100 mA cm−2. For the full cell overall water splitting performance, cell overpotentials as low as 140 and 151 mV were needed to drive 10 mA cm-2 in seawater and alkaline solution electrolytes.

Green ammonia production using current and emerging electrolysis technologies

This study investigates utilizing hydrogen produced via water electrolysis to produce green ammonia. Routes are benchmarked based on employing either alkaline electrolysis (AEC) or solid oxide electrolysis (SOEC). Both existing and possible improvements are modeled for the AEC and SOEC technologies coupled with the Haber-Bosch process to synthesize ammonia. The cost of green ammonia is estimated considering the cost of electrolyzers for both today and future projections and are compared with that of "fossil" ammonia synthesized from natural gas. Threshold CO2 taxes required to achieve cost parity between green and "fossil" ammonia are determined based on the price of natural gas and the levelized cost of electricity. It is found that whereas the green ammonia produced from a system based on AEC is cheaper today, SOEC shows to be more cost-effective, when basing the comparison on the projected future cost of the electrolyzers. Green ammonia from an SOEC-based plant is estimated to have accost of 495 €/t by 2050 with an assumed electricity price of 30 €/MWh. In the SOEC-based ammonia plants, approximately 57 % and 31 % of the steam needed for the electrolyzers can be generated through heat integration between the electrolyzer and Haber-Bosch process, for low-pressure and high-pressure electrolyzers, respectively. A good fraction of the heat can also be covered by the intercoolers of the compressors. With the projected cost for SOEC, reducing the levelized cost of electricity from 60 to 10 €/MWh would decrease the cost of green ammonia from 690 to 340 €/t by 2050.

Bimetallic Ni and Pt single atoms anchored on nitrogen–phosphorus doped porous carbon fibers to achieve significant electrocatalytic hydrogen evolution

The commercial application of water electrolysis for hydrogen production requires the development of low precious metal catalysts with a high crustal abundance. One feasible strategy is to utilize bimetallic catalysts composed of both transition and precious metals. In this study, a novel N/P-doped Ni/Pt bimetallic catalyst is developed (NiPt@C-NP, 3.68 % Ni, 0.2 % Pt) using polyacrylonitrile fibers as an inexpensive carbon source for catalyst support. Due to strong anchoring from the N and P heteroatoms, the nickel and platinum species are mono-atomically dispersed throughout the catalyst. Under acidic conditions, NiPt@C-NP exhibits a hydrogen evolution overpotential of 89 mV (10 mA cm−2), whereas an unsupported platinum catalyst gives an overpotential of 302 mV. The mass activity of Pt in NiPt@C-NP reaches 36.17 A mgPt−1, which is 33 times higher than 20 % Pt/C (1.07 A mgPt−1). Density functional theory (DFT) calculations reveal that synergistic interactions between Ni and Pt significantly increase the density of state near the Fermi level of NiPt@C-NP, resulting in a reduced bandgap and an enhanced charge transfer capability. Furthermore, the Gibbs free energy at the Pt and Ni sites is − 0.25 and − 0.63 eV, respectively, indicating fast reaction kinetics.

Dumbbell-Shaped, Block-Graft Copolymer with Aligned Domains for High-performance Hydrocarbon Polymer Electrolyte Membranes.

Given the environmental concerns surrounding fluoromaterials, the use of high-cost perfluorinated sulfonic acids (PFSAs) in fuel cells and water electrolysis contradicts the pursuit of clean energy systems. Herein, we present a fluorine-free dumbbell-shaped block-graft copolymer, derived from the cost-effective triblock copolymer poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS), for polymer electrolyte membranes (PEMs). This unique polymer shape led to the alignment of the hydrophobic-hydrophilic domains along a preferred orientation, resulting in the construction of interconnected proton channels across the membrane. A bicontinuous network allowed efficient proton transport with reduced tortuosity, leading to an exceptional ionic conductivity (249 mS cm-1 at 80 °C and 90% relative humidity (RH)), despite a low ion exchange capacity (IEC; 1.41). Furthermore, membrane-electrode assembly (MEA) prepared with our membrane exhibited stable performance over a period of 150 h at 80 °C and 30% RH. This study demonstrates a novel polymer structure design and highlights a promising outlook for hydrocarbon PEMs as alternatives to PFSAs.

Dumbbell‐Shaped, Block‐Graft Copolymer with Aligned Domains for High‐performance Hydrocarbon Polymer Electrolyte Membranes

Given the environmental concerns surrounding fluoromaterials, the use of high‐cost perfluorinated sulfonic acids (PFSAs) in fuel cells and water electrolysis contradicts the pursuit of clean energy systems. Herein, we present a fluorine‐free dumbbell‐shaped block‐graft copolymer, derived from the cost‐effective triblock copolymer poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS), for polymer electrolyte membranes (PEMs). This unique polymer shape led to the alignment of the hydrophobic‐hydrophilic domains along a preferred orientation, resulting in the construction of interconnected proton channels across the membrane. A bicontinuous network allowed efficient proton transport with reduced tortuosity, leading to an exceptional ionic conductivity (249 mS cm‐1 at 80 °C and 90% relative humidity (RH)), despite a low ion exchange capacity (IEC; 1.41). Furthermore, membrane‐electrode assembly (MEA) prepared with our membrane exhibited stable performance over a period of 150 h at 80 °C and 30% RH. This study demonstrates a novel polymer structure design and highlights a promising outlook for hydrocarbon PEMs as alternatives to PFSAs.

Organic Electrode Materials for Energy Storage and Conversion: Mechanism, Characteristics, and Applications.

ConspectusLithium ion batteries (LIBs) with inorganic intercalation compounds as electrode active materials have become an indispensable part of human life. However, the rapid increase in their annual production raises concerns about limited mineral reserves and related environmental issues. Therefore, organic electrode materials (OEMs) for rechargeable batteries have once again come into the focus of researchers because of their design flexibility, sustainability, and environmental compatibility. Compared with conventional inorganic cathode materials for Li ion batteries, OEMs possess some unique characteristics including flexible molecular structure, weak intermolecular interaction, being highly soluble in electrolytes, and moderate electrochemical potentials. These unique characteristics make OEMs suitable for applications in multivalent ion batteries, low-temperature batteries, redox flow batteries, and decoupled water electrolysis. Specifically, the flexible molecular structure and weak intermolecular interaction of OEMs make multivalent ions easily accessible to the redox sites of OEMs and facilitate the desolvation process on the redox site, thus improving the low-temperature performance, while the highly soluble nature enables OEMs as redox couples for aqueous redox flow batteries. Finally, the moderate electrochemical potential and reversible proton storage and release of OEMs make them suitable as redox mediators for water electrolysis. Over the past ten years, although various new OEMs have been developed for Li-organic batteries, Na-organic batteries, Zn-organic batteries, and other battery systems, batteries with OEMs still face many challenges, such as poor cycle stability, inferior energy density, and limited rate capability. Therefore, previous reviews of OEMs mainly focused on organic molecular design for organic batteries or strategies to improve the electrochemical performance of OEMs. A comprehensive review to explore the characteristics of OEMs and establish the correlation between these characteristics and their specific application in energy storage and conversion is still lacking.In this Account, we initially provide an overview of the sustainability and environmental friendliness of OEMs for energy storage and conversion. Subsequently, we summarize the charge storage mechanisms of the different types of OEMs. Thereafter, we explore the characteristics of OEMs in comparison with conventional inorganic intercalation compounds including their structural flexibility, high solubility in the electrolyte, and appropriate electrochemical potential in order to establish the correlations between their characteristics and potential applications. Unlike previous reviews that mainly introduce the electrochemical performance progress of different organic batteries, this Account specifically focuses on some exceptional applications of OEMs corresponding to the characteristics of organic electrode materials in energy storage and conversion, as previously published by our groups. These applications include monovalent ion batteries, multivalent ion batteries, low-temperature batteries, redox flow batteries with soluble OEMs, and decoupled water electrolysis employing organic electrodes as redox mediators. We hope that this Account will make an invaluable contribution to the development of organic electrode materials for next-generation batteries and help to unlock a world of potential energy storage applications.

Synthesis of nitrogen and sulfur bi-doped carbon obtained from spent sapelli wood sawdust and polyhydric alcohol with improved catalytic activity for hydrogen evolution reaction

Developing an efficient water electrolysis system is an important solution for on the development of highly active, cost-effective, and stable electrocatalysts. Carbon-based metal-free catalysts are one of the promising candidates for this purpose. Herein, we present a facile strategy to synthesize and characterize nitrogen and sulfur co-doped porous carbon (NS-PC) from spent sapelli wood sawdust and polyhydric alcohol (xylitol) for efficient hydrogen evolution reaction (HER) in alkaline electrolyte. The resultant NS-PC metal-free catalyst exhibits porous structure, high surface areas and enhanced HER performance with lowest Tafel slope of 68.1 mV dec−1. The enhanced performance is due to the high porosity of carbonaceous material and co-existence of active species (N in the forms of graphitic-N, pyridinic-N, pyrrolic-N, and S in the forms of C–S–C) induced by the maximum carbon-carbon bond polarization, charge re-distribution in the carbon matrices with a synergistically HER activity. In addition, this work provides a versatile and effective strategy for synthetizing excellent carbon-based metal free catalysts from the low cost biowaste for large-scale production of hydrogen through HER.

The Cost Reduction Analysis of Green Hydrogen Production from Coal Mine Underground Water for Circular Economy

The novelty of the paper is the analysis of the possibilities of reducing the operating costs of a mine water pumping station in an abandoned coal mine. To meet the energy needs of the pumping station and reduce the carbon footprint, “green” energy from a photovoltaic farm was used. Surplus green energy generated during peak production is stored in the form of green hydrogen from the water electrolysis process. Rainwater and process water are still underutilized sources for increasing water resources and reducing water stress in the European Union. The article presents the possibilities of using these waters, after purification, in the production of green hydrogen by electrolysis. The article also presents three variants that ensure the energy self-sufficiency of the proposed concepts of operation of the pumping station.