Electrocatalytic Water Research Articles

Breaking barriers in electrocatalysis: unleashing the power of highly efficient Mn/CoS@S-g-C3N4 nanocomposite for electrocatalytic water splitting and superior H2 production

Breaking barriers in electrocatalysis: unleashing the power of highly efficient Mn/CoS@S-g-C3N4 nanocomposite for electrocatalytic water splitting and superior H2 production

Synthesis Framework for Designing PtPdCoNiMn High-Entropy Alloy: A Stable Electrocatalyst for Enhanced Alkaline Hydrogen Evolution Reaction.

High entropy alloys (HEAs) are an emerging class of advanced materials characterized by their multifunctionality and potential to replace commercial catalysts in electrocatalytic water splitting. The synergy among the various alloyed elements in HEAs makes them particularly promising for applications in electrocatalysis. However, preparation of HEA via bottom-up approaches by avoiding the formation of mono, di, and tri metallic alloys in the nanoscale is challenging. This aspect is addressed, in this study by exploring the logical selection of solvents, reducing agents, and capping agents, along with their relative fractions, in the solvothermal synthesis of the HEA comprising platinum-palladium-cobalt-nickel-manganese (PtPdCoNiMn). It is established that the reducing capabilities of both the solvent and reducing agent are crucial for the reduction of each metal to form a single-phase HEA. The synthesized HEA (20 wt.%)/functionalized carbon (FC) demonstrates excellent performance as an HER catalyst, exhibiting a low overpotential of 48.7mV at -10 mA cm-2 in an alkaline electrolyte. This performance is characterized by high reaction kinetics and stability at elevated current densities. Furthermore, the catalyst shows impressive performance in both simulated and actual seawater. This development reduces the reliance on platinum while enhancing the long-term durability and catalytic efficiency of the electrocatalyst.

Unveiling N-doped carbon nitride aerogel for efficient electrocatalytic water splitting application

Unveiling N-doped carbon nitride aerogel for efficient electrocatalytic water splitting application

Surface Sulfurization of Cubic Cu2O to Form Cu2S Nanostructure-Decorated Catalysts for Light-enhanced Electrocatalytic H2 Evolution and Photocatalytic CO2 Reduction.

Developing highly efficient bifunctional catalysts for electrocatalysis and photocatalysis suffers from sluggish charge transfer and poor photo-to-electric conversion rate. Herein, micro-sized Cu2O cubes were initially prepared for subsequent transformation into Cu2O@Cu2S core-shell structures by a slight surface sulfurization. The formation of nanostructured Cu2S thin layer at Cu2O surface can endow an immediate charge separation and migration under light irradiation, leading to high surface photovoltages (SPV, 18-30 mV). As a result, the as-prepared Cu2O@Cu2S catalysts exhibited reduced overpotentials (η, only 86 mV is required for the optimized sample to achieve a current density of 10 mA cm-2) for H2 evolution with good cycling stability in electrocatalytic water splitting. Meanwhile, a high methane (CH4) production rate of 30.3 μmol h-1 g-1 can be delivered from the optimized Cu2O@Cu2S sample when used for photocatalytic CO2 reduction. This work has provided a strategy to prepare bifunctional catalysts with improved photoelectric properties for photo/electrocatalytic applications.

Low-Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation.

Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin-state manipulation holds great promise to break through this bottleneck. Low-spin Fe3+ (LS, t2g 5eg 0) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe3+ in NiFe-layered double hydroxide (NiFe-LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their d orbital splitting energy. The as-obtained catalyst exhibits extraordinary OER performance with an ultra-low overpotential of 244 mV at the industrially required current density of 500 mA cm-2, which is 110 mV lower than that of the conventional NiFe-LDH with high-spin Fe3+ (HS, t2g 3eg 2) and superior to most previously reported NiFe-based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe3+ configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate-determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin-dependent electrocatalysts for OER and beyond.

Partial Selenization Strategy for Fabrication of Ni0.85Se@NiCr-LDH Heterostructure as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

NiCr-LDH and its partial selenization as Ni0.85Se@NiCr-LDH heterostructure is established here as an alkaline water electrolyzer for achieving enhanced overall water splitting efficiency. The hydrothermally synthesized optimized batch of Ni0.85Se@NiCr-LDH is thoroughly characterized to elucidate its structure, morphology, and composition. Compared to pristine NiCr-LDH, the batch of Ni0.85Se@NiCr-LDH exhibits exceptional alkaline OER and HER activity with low overpotentials of 258 and 85 mV at 10 mA cm-2, respectively. Besides, Ni0.85Se@NiCr-LDH also exhibits excellent acidic HER with an overpotential of only 61 mV at 10 mA cm-2, indicating that Ni0.85Se@NiCr-LDH can operate effectively across a wide pH range. The excellent electrochemical stability of Ni0.85Se@NiCr-LDH for 24 h operation is attributed to the formation of a thin layer of SeOx during OER operation. The role of selenization and the effect of Cr in the LDH lattice toward enhanced electrocatalytic water splitting is discussed. The outstanding OER and HER performances of Ni0.85Se@NiCr-LDH are attributed to the higher electrochemical active surface area, favorable conditions for adsorption of HER/OER intermediates, low charge transfer resistance, and improved conductivity. The practical application ofNi0.85Se@NiCr-LDHas a bifunctionalelectrocatalyst for overall water splitting is reflected from the low cell voltage of 1.548 V at 10 mA cm-2.

Lewis acid sites in hollow cobalt phytate micropolyhedra promote the electrocatalytic water oxidation.

The acid-base microenvironment of the metal center is crucial for constructing advanced oxygen evolution reaction (OER) electrocatalysts. However, the correlation between acidic site and OER performance remains unclear for cobalt-based catalysts. Herein, Lewis acid sites in hollow cobalt phytate micropolyhedra (M-CoPA, M = Cu, Sr) were synthesized by a cation-exchange strategy, and their OER performances were studied systematically. Experimentally, Lewis acid Cu2+ sites with stronger Lewis acidity exhibited superior intrinsic activity and long-term stability in alkaline electrolytes. The spectroscopic and electrochemical studies show Lewis acid sites in hollow cobalt phytate micropolyhedra can modulate the electronic distribution of the adjacent cobalt center and further optimize the adsorption strength of oxygenated species. This study figures out the effect of Lewis acid sites on the OER kinetics and provides an effective way to develop high-efficiency electrocatalysts for energy conversion systems.

Enhanced oxygen evolution reaction in flexoelectric thin-film heterostructures

Recently, the flexoelectric effect has triggered considerable interest in energy-related applications, such as flexo-actuation, flexo-photovoltaic, and flexo-catalysis, because of its ubiquitous feature allowing the creation of electric polarity, i.e., the flexoelectric polarization (Pflexo), in non-polar materials by strain gradient. Here, we show a flexoelectric strategy in electrocatalytic water splitting. Remarkably enhanced oxygen evolution reaction (OER) properties are achieved in strain-gradient LaFeO3 (LFO) thin-film heterostructures owing to the promotion of kinetic processes by Pflexo. The improved OER is demonstrated by increased current density of ∼300% in linear sweep voltammetry and lowered charge transfer resistance by two orders of magnitude in electrochemical impedance spectroscopy. These are ascribed to the flexoelectric-induced downward bending of the LFO band, as revealed by density functional theory calculations and band structure measurements. With Pflexo in the thin-film heterostructure catalysts, the adsorption of hydroxyl ions is strengthened on the polar LFO surface, and the transfer of electrons is accelerated from the reactants/key intermediates to the catalyst across the band-tilted LFO layer. These findings indicate the significance of flexoelectric effect in OER kinetics and open a new perspective for exploiting catalytic mechanisms and performances in water splitting.

Combined effect of nitrogen-doped carbon and NiCo2O4 for electrochemical water splitting

Electrocatalytic water splitting for green hydrogen production necessitates effective electrocatalysts. Currently, commercial catalysts are primarily platinum-based. Therefore, finding catalysts with comparable catalytic activity but lower cost is essential. This paper describes spinel-structured catalysts containing nickel cobaltite NiCo2O4, graphene, and additionally doped with heteroatoms. The structure and elemental composition of the obtained materials were analyzed by research methods such as TEM, SEM-EDX, XRD, XPS, and Raman spectroscopy. The electrochemical measurements showed that hybrid materials containing nickel cobaltite NiCo2O4 doped with graphene are highly active catalysts in the hydrogen evolution reaction (Tafel slopes = 91 mV dec−1, overpotential = 468 mV and onset potential = -339 mV), while in the oxygen evolution reaction (Tafel slopes = 51 mV dec−1, overpotential = 1752 mV and onset potential = 370 mV), bare NiCo2O4 without the addition of carbon has a worse activity (for HER: Tafel slopes = 120 mV dec−1, overpotential - does not achieve and onset potential = -404 mV, for OER: Tafel slopes = 54 mV dec−1, overpotential = 1796 mV and onset potential = 410 mV). In terms of stability, comparable results were obtained for each synthesized compound for both the HER and OER reactions.

Composite shell empowered crystalline-amorphous NiO/NiWO4-rGO core-shell electrocatalyst for efficient water electrocatalysis

Composite shell empowered crystalline-amorphous NiO/NiWO4-rGO core-shell electrocatalyst for efficient water electrocatalysis

Reinforcement of electrocatalytic overall water splitting by constructing Mo-doped NiFe LDH/NiS heterostructure

Electrochemical water splitting is considered to be an environmentally friendly and efficient method of hydrogen production. NiFe LDH is a well-known electrocatalyst for oxygen evolution, yet its effectiveness in HER has been suboptimal. In this research, we created a Mo-NiFe LDH@NiS catalyst on carbon cloth via cation doping and heterointerface construction of NiFe LDH. The resulting Mo-NiFe LDH@NiS/CC showed remarkable HER activity. Furthermore, when used as a bifunctional electrode for overall water splitting, Mo-NiFe LDH@NiS/CC operated at a cell voltage of 1.58V at a current density of 10mA/cm² and exhibited outstanding durability. This study emphasizes the significant enhancement in HER and overall water-splitting efficiency of NiFe LDH achieved through Mo doping and heterostructure engineering, advancing its potential for effective water splitting applications.

NiMo/NiFe-LDH heterostructured electrocatalyst for hydrogen production from water electrolysis

Constructing low-cost and efficient catalysts for electrocatalytic water splitting to produce hydrogen is of great significance. In this study, we successfully prepared NiMo/NiFe-LDH electrocatalysts with abundant coupled interfaces using a hydrothermal method and electrodeposition. The synergistic effect between the NiMo alloy and NiFe-LDH nanosheets induces charge redistribution at the interface and accelerates charge transfer, thus improving reaction kinetics and enhancing electrocatalytic performance. Experimental results show that at a current density of 10 mA cm−2, the HER overpotential of NiMo/NiFe-LDH is 35 mV, demonstrating excellent water-splitting performance. This work provides insights into the development of alloy/transition metal hydroxides for efficient water-splitting hydrogen production

Photothermally enhanced electrocatalytic water splitting with iron-doped nickel phosphide

Photothermally enhanced electrocatalytic water splitting with iron-doped nickel phosphide

Engineering the Coordination Environment in the Silver(I)- and Ruthenium(II)-N-Heterocyclic Carbene Complexes in Instigating the Electrocatalytic Hydrogen Evolution Reaction.

The quest for cost-efficient and high-performance electrocatalysts towards electrocatalytic water splitting is a key and an interdisciplinary area of study. Considerable progress is being driven by developments in the field of energy research. In a fundamental study, we have synthesized NHC precursors (6 and 7) and corresponding metal-NHC complexes of silver(I)- (8 and 9) and ruthenium(II)- (10 and 11) of a N-heterocyclic carbene-based ligand type incorporating coumarins. These NHC precursors and metal-NHC complexes were characterized through various analytical and spectral techniques. The silver(I)-NHC complexes 8 and 9 displayed a linear coordination geometry with a center of inversion, which is evidenced by the single-crystal X-ray diffraction technique. Both the series of complexes were assessed for their efficacies in the hydrogen evolution reaction (HER). The results demonstrated that attributed to its peculiar coordination geometry, high electrical conductivity the silver(I)- and ruthenium(II)-NHC complexes exhibited exemplary electrocatalytic activity. Activities of the hydrogen evolution reaction on two differently modified electrode substrates with metal-NHC complexes have been studied. To attain the benchmark HER current density of 10 mA cm-2, in 1.0 M KOH, an overpotential of -375 to -527 mV vs RHE was required for the metal-NHC complexes. Based on the analysis of the Tafel slope values, the rate-determining step was the adsorption of hydrogen as investigated in the potential window. The molecular electrocatalyst 10 presented a superior stability and maintained the electrocatalytic activity for a duration of 18 h with complex 8 and 24 h with respect to complex 10 in 1.0 M KOH. Apace with these studies, hydrogen oxidation studies were examined in 0.5 M H2SO4 by a substantial current density at the platinum ring electrode. This research offers feasible guidance for developing organometallic-based molecular electrocatalysts with good electrocatalytic performance.

Novel Gel method MXene-Supported Dual-Site PtNi-NiO for Electrocatalytic Water Reduction and Urea Oxidation.

Compared to the traditional oxygen evolution reaction (OER), the urea oxidation reaction (UOR) generally exhibits a lower overpotential during the electrolytic process, which is conducive to the hydrogen evolution reaction (HER) at the cathode. The superior structure and abundant sites play a crucial role in promoting the adsorption and cleavage of urea molecules. Therefore, this paper introduces a simple metal cation-induced gelation method to prepare an electrocatalyst with PtNi alloy-NiO dual sites supported on Ti3C2Tx, which simultaneously exhibits excellent UOR and HER performance. PtNi-NiOx/Ti3C2Tx demonstrates good catalytic activity for the urea oxidation reaction, requiring only 1.364V (overpotential of 0.994V) to achieve a current density of 100mAcm-2 in UOR, and also exhibits remarkable catalytic activity in the hydrogen evolution reaction, with PtNi-NiOx/Ti3C2Tx achieving a current density of 10mAcm-2 in HER with only 24mV of overpotential. In the UOR//HER two-electrode electrolysis cell, it requires only 1.361 and 1.538V to reach current densities of 10 and 100mAcm-2, respectively. According to density functional theory (DFT) calculations, the dual active sites can intelligently adsorb the electron-donating/electron-withdrawing groups in urea molecules, activate chemical bonds, and thereby initiate urea decomposition.

Research Progress on Clay‐Based Materials for Electrocatalytic Water Splitting

AbstractClay‐based materials are an emerging family of earth‐abundant and low‐cost inorganic functional materials with an modifiable layered‐structure mode similar to hydroxides. They are considered as competitive electrocatalysts for water splitting due to their variable intra‐layer ions, exchangeable interlayer molecules/ions, and large reaction surfaces, which demonstrate fascinating engineering opportunities at the microscale, mesoscale, and macroscale levels. We systematically summarized the research progress of clay‐based materials by classifying clay‐like compounds, clay‐based composites, and clay‐based derivatives, from the viewpoint of structural geometries towards optimizing functionalities. The design strategies for regulating and optimizing clay‐based materials to meet the requirements of electrocatalysts with excellent activity and stability were outlined through representative examples. In addition, the hydrogen production applications of these clay‐based materials were discussed reasonably including recent advances. Finally, the future perspectives of clay‐based materials for electrocatalytic water splitting were demonstrated.

Metal Imidazole-Modified Covalent Organic Frameworks as Electrocatalysts for Alkaline Oxygen Evolution Reaction.

Since the product contains no carbon-based substances and can be driven by non-carbon-based electricity, electrocatalytic water splitting is considered to be among the most effective strategies for alleviating the energy crisis and environmental pollution. This process helps lower greenhouse gas emissions while also supporting the shift toward renewable energy sources. The anodic oxygen evolution reaction (OER) involves a more complex multi-electron transfer process, which is the principal limiting factor in overall water splitting. Extensive research has demonstrated that the controlled design of effective electrocatalysts can address this limitation. In this study, a previously unreported covalent organic framework material (COF-IM) was synthesized via a post-synthetic modification strategy. Notably, COF-IM contains imidazole nitrogen metal active sites. Transition metal-coordinated COF-IM@Co can function as a highly effective electrocatalyst, exhibiting a lower overpotential (403.8 mV@10 mA cm-2) in alkaline electrolytes, thereby highlighting its potential for practical applications in energy conversion technologies. This study offers new perspectives on the design and synthesis of COFs, while also making substantial contributions to the advancement and application of OER electrocatalysts.

Nickel Hydroxysulfide Electrocatalyst Promotes Urea Oxidation for Energy‐Saving Hydrogen Production

AbstractThe occurrence of oxygen evolution reaction (OER) almost consumes most of the electric energy of hydrogen production by electrocatalytic water splitting. The energy required in the process of electrochemical hydrogen production can be reduced by choosing urea oxidation reaction (UOR) instead of OER. In this work, nickel hydroxysulfide is synthesized on nickel foam (NiSOH/NF) and its electrocatalytic performance was tested in UOR. Experimental results show that the vulcanization catalyst requires a low potential of 1.38 V (vs RHE) to achieve a current density of 100 mA cm−2 in an electrolyte containing 0.5 M urea, which is 270 mV lower than the conventional OER process. This innovative approach has yielded a substantial reduction in the cell voltage necessary for overall water splitting under two electrode system, thereby enhancing its efficiency and feasibility.

Interface Engineering Induced by Low Ru Doping in Ni/Co@NC Derived from Ni-ZIF-67 for Enhanced Electrocatalytic Overall Water Splitting.

Electrochemical water splitting is a promising approach for hydrogen evolution reactions (HER); however, the oxygen evolution reaction (OER) remains a major bottleneck due to its high energy requirements. High-performance electrocatalysts capable of facilitating HER, OER, and overall water splitting (OWS) are highly needed to improve OER kinetics. In this work, we synthesized a trimetallic heterostructure of Ru, Ni, and Co incorporated into N-doped carbon (denoted as Ru/Ni/Co@NC) by first synthesizing Ni/Co@NC from Ni-ZIF-67 polyhedrons via high-temperature carbonization, followed by Ru doping using the galvanic replacement method. Benefiting from increased active surface sites, modulated electronic structure, and enhanced interfacial synergistic effects, Ru/Ni/Co@NC exhibited exceptional electrocatalytic performance for both HER and OER processes. The optimized Ru/Ni/Co@NC catalyst, with a minimal Ru mass ratio of ∼2.07%, demonstrated significantly low overpotential values of 34 mV for HER and 174 mV for OER at a current density of 10 mA/cm2 with corresponding Tafel slope values of 33.42 and 34.39 mV/dec, respectively. Further, the optimized catalyst was loaded onto carbon paper and used as anode and cathode materials for alkaline water splitting. Interestingly, a low cell voltage of just 1.44 V was obtained. The enhanced electrolytic performance was further elaborated by density functional theory (DFT) calculations, which confirmed that Ru doping in Ni/Co introduced additional active sites for H*, enhancing adsorption/desorption abilities for HER (ΔGH* = -0.30 eV), lowering water dissociation barrier (ΔGb = 0.49 eV) and reducing the energy barrier for the rate-determining step of OER (O* → OOH*) to 1.62 eV in an alkaline environment. These findings reflect the significant potential of ZIF-67-based catalysts in energy conversion and storage applications.

Band Engineering of Mn-P Alloy Enables HER-suppressed Aqueous Manganese Ion Batteries.

Aqueous manganese ion batteries hold potential for stationary storage applications owing to their merits in cost, energy density, and environmental sustainability. However, the formidable challenge is the instability of metallic manganese (Mn) anodes in aqueous electrolytes due to severe hydrogen evolution reaction (HER), which is more serious than the commonly studied Zn metal anodes. Moreover, the mechanism of HER side reactions has remained unclear. Herein, we design a series of Mn-P alloying anodes by precisely regulating their energy band structures to mitigate the HER issue. It is found that the serious HER primarily originates from the spontaneous Mn-H2O reaction driven by the excessively high HOMO energy level of Mn, rather than electrocatalytic water splitting. Owing to a reduced HOMO energy level and enhanced electron escape work function, the MnP anode achieves an evidently enhanced cycle durability (over 1000 hours at a high current density of 5 mA cm-2). The MnP||AgVO full cell with an N/P ratio of 4 exhibits better rate capability and extended cycle life (7000 cycles) with minimal capacity degradation than the cell using metallic Mn anode (less than 100 cycles). This study provides a practical approach for developing highly durable aqueous Mn ion batteries.