Non-precious Metal Research Articles

Electrochemical alcohol oxidation reaction on Precious‐Metal‐Free catalysts: Mechanism, activity, and selectivity

AbstractThe electrochemical alcohol oxidation reaction (AOR) is pivotal for the development of sustainable energy. The complete oxidation of alcohols has attracted extensive attention as a vital process in fuel cells. Moreover, as an alternative reaction to the oxygen evolution reaction, the selective oxidation of alcohols emerges as an effective means to lower the energy expenditure associated with electrolytic hydrogen production while yielding high‐value products. Nonprecious metal materials have been widely applied in the selective oxidation catalysis of alcohols due to their cost‐effectiveness and excellent durability. In recent years, leveraging the advantages of nonprecious metal materials in electrocatalytic AOR, researchers have delved into catalytic mechanisms and various efficient catalysts have been fabricated and evaluated. This review provides an overview of the current advancements in the electrocatalytic selective oxidation of diverse alcohols and the catalytic systems centered around nonprecious metal materials. It systematically summarizes the shared traits and distinctions in catalytic reaction characteristics across various systems, thereby laying the theoretical foundation for developing novel catalyst systems that are efficient, stable, and highly selective. This review will facilitate the utilization of nonprecious metal catalysts further toward the electrocatalytic oxidation of alcohols.

Modulating the electron interaction of Cu-Ni hybrid sites for boosting photocatalytic hydrogen evolution over Al-doped SrTiO3

Cocatalysts play a pivotal role in enhancing the efficiency of photocatalytic water splitting. In this study, we introduced a novel and straightforward pre-impregnation strategy to anchor a CuNi dual cocatalyst onto the surface of Al-doped SrTiO3 (Al-STO), coupled with photodeposition. This approach led to a remarkable 11.07-fold (77.5 µmol/h) increase in hydrogen evolution performance compared to the conventional photodeposition method for decorating with CuNi dual cocatalysts. Not only that, after the 18 h cycle experiment, the catalyst still maintains high activity and high stability similar to that of precious metals, which overcomes the defects of poor stability and short life of non-precious metals. This strategy capitalizes on the pre-adsorption of cocatalyst precursor ions on the Al-STO support via impregnation, enhancing both the adsorption energy and capacity between the precursor ions and the active sites. Detailed characterizations have revealed a strong electronic interaction within the Cu-Ni structure and improved interfacial coupling between CuNi and Al-STO. This not only significantly promotes charge separation and transfer but also provides a plethora of active sites for the photocatalytic generation of H2. Moreover, extensive theoretical calculations have provided deep insights into the reaction mechanism of the CuNi system and elucidated the reasons behind the varying degrees of activity enhancement across different cocatalyst architectural systems.

Preparation and application research of transition metal phosphides

Due to the serious environmental pollution in the world, the shortcut to harmonious development is to improve traditional disposable energy and identify new energy sources that can be utilized. The current problem that human society must solve is to discover and use efficient and inexhaustible new energy sources, among which electrolytic water technology is an effective way to develop clean energy. In recent years, researchers have focused on producing hydrogen by electrolyzed water, but the intermediate hydrogen evolution reaction and the oxygen evolution reaction are relatively slow kinetic processes, and they cannot give the factory a large range of electrolytic water hydrogen production work and push down the commercialization process, so improving the rate of electrolytic water process must be an efficient catalyst. Transition metal phosphide is one of the non-precious metal catalysts in the electrochemical hydrogen evolution reaction and oxygen evolution reaction. Transition metal phosphide can promote rapid change of chemical reaction rate, and it has the characteristics of being cheap and easy to operate so it has a great prospect in the electrolysis of water. In this experiment, the oxygen evolution performance was optimized based on the crystal surface regulation of cobalt-doped transition metal nickel phosphide. The optimal reduction time and a small overpotential (60 mV) were obtained by using sodium borohydride to reduce the sample.

Lithium-Induced Oxygen Vacancies in MnO2@MXene for High-Performance Zinc-Air Batteries.

The traditional methods for creating oxygen vacancies in materials present several challenges and limitations, such as high preparation temperatures, limited oxygen vacancy generation, and morphological destruction, which hinder the application of transition metal oxides in the field of zinc-air batteries (ZABs). In order to address these limitations, we have introduced a pioneering lithium reduction strategy for generating oxygen vacancies in δ-MnO2@MXene composite materials. This strategy stands out for its simplicity of implementation, applicability at room temperature, and preservation of the material's structural integrity. This research demonstrates that aqueous Ov-MnO2@MXene-5, with introduced oxygen vacancies, exhibits an outstanding oxygen reduction reaction (ORR) activity with an ORR half-wave potential reaching 0.787 V. DFT calculations have demonstrated that the enhanced activity could be attributed to adjustments in the electronic structure and alterations in adsorption bond lengths. These adjustments result from the introduction of oxygen vacancies, which in turn promote electron transport and catalytic activity. In the context of zinc-air batteries, cells with Ov-MnO2@MXene-5 as the air cathode exhibit outstanding performance, featuring a significantly improved maximum power density (198.3 mW cm-2) and long-term cycling stability. Through the innovative strategy of introducing oxygen vacancies, this study has successfully enhanced the electrochemical catalytic performance of MnO2, overcoming the limitations associated with traditional methods for creating oxygen vacancies. Consequently, this research opens up new avenues and directions for nonprecious metal catalyst application in ZABs.

Tuning Cu2O morphologies of Cu2O/Ni foam electrodes for the control of reactivity and nitrogen selectivity in direct ammonia electrooxidation reaction

Direct electrochemical oxidation of ammonia (AEO) using non-precious metal catalysts is an energy-efficient and low-carbon-footprint method for ammonia removal from wastewater. In this work, Cu2O with three types of morphologies, including flower, particle, and sheet, were electrodeposited on Ni foam substrates (Cu2O/NF) for direct AEO. The Cu2O flower-deposited NF electrode showed the largest electrochemical surface area (19.6 cm2) and the smallest Cu2O size (200–600 nm) among all Cu2O/NF electrodes. In the ammonia solution, the peak current densities of direct AEO from cyclic voltammograms (CVs) at 10 mVs−1 on the Cu2O flower, Cu2O particle, and Cu2O sheet-deposited NF electrodes reached 4.6, 3.1, and 2.2 mAcm−2, respectively. The result showed that, at an initial pH of 11 and an applied potential of 0.95 V vs. Hg/HgO, the order of three types of Cu2O morphologies with respect to ammonia removal efficiency and rate is: Cu2O flower (52%, 4.1×10−3 min−1) > Cu2O particle (38%, 2.6×10−3 min−1) > Cu2O sheet (30%, 1.8×10−3 min−1). Interestingly, ammonia oxidation to N2 on the Cu2O sheet-deposited NF electrode exhibited the highest selectivity (SN2: 60%), which was much higher than the Cu2O flower-deposited NF electrode (SN2: 31%). The high SN2 of Cu2O sheets was ascribed to the presence of the stable Cu(I) sheet structure during direct AEO, confirmed by X-ray photoelectron spectroscopy analysis. On the other hand, the Cu(II)-rich flower structure facilitated the formation of NO3-. Our findings demonstrate that the surface morphologies of Cu2O deposited on the NF electrode show significant stability difference of Cu(I), which determines reactivity and N selectivity during direct AEO.

The dependence of electrocatalytic HER activity of decorated MoS2 with Cu nanoclusters

Molybdenum disulfide is a potential electrocatalytic material for water splitting with excellent stability and durability. Here, the electrocatalytic hydrogen evolution reaction performance of Molybdenum disulfide nanosheets decorated with copper nanoclusters was investigated. The Cu@MoS2–1:10 exhibited remarkable hydrogen evolution reaction activity, with an overpotential as low as 150 mV under acidic conditions. The First-principles calculations further confirmed the superior electrocatalytic performance of Cu@MoS2, with a minimum hydrogen adsorption free energy of -0.10 eV. The improved electrocatalytic activity of Cu@MoS2 arises from the accelerated charge migration at the interface. And the addition of Cu increases the number of active sites on the surface of MoS2. This work could offer insights into the advancement of additional non-precious metals and transition metal dichalcogenides.

Synergistic effects of fluorine and nitrogen dopants in fluorine/nitrogen-coordinated iron-co-doped carbon catalysts for enhanced oxygen reduction in alkaline media

The expensiveness of oxygen reduction reaction (ORR) catalyst materials especially Pt has hindered the commercialization of next-generation energy conversion devices including metal–air batteries and polymer electrolyte membrane fuel cells. Fe–N–C has drawn attention as a nonprecious metal catalyst owing to its high but commercially unsatisfactory ORR performance; nevertheless, additional heteroatom co-doping could help augment its ORR activity. Here we report nitrogen/fluorine-coordinated iron-co-doped carbon (Fe@NFC) catalysts with improved ORR performance in alkaline media. The annealing temperature affects the nitrogen/fluorine doping and functional group formation, as ascertained by an analysis of control samples annealed at various temperatures. To assess the synergy between the doped fluorine and nitrogen-coordinated iron, we compare the catalyst annealed at 700 °C (Fe@NFC700) with control samples containing different heteroatom dopants but annealed at 700 °C (Fe@NC, Fe@FC). Fe@NFC700 shows improved ORR kinetics and onset potential than those of Fe@NC and commercial Pt/C, respectively, in alkaline media.

One-step synthesis of seamlessly contacted non-precious metal cocatalyst modified CdS hollow nanoflowers spheres for photocatalytic hydrogen production

This study ingeniously synthesized a novel CdS/NiS hollow nanoflower sphere (HNS) using a one-step method to enhance photocatalytic hydrogen production activity. Compared to conventional preparation methods, this approach features seamlessly interfaced contact that facilitates efficient electron transfer across the interface. The internal hollow structure allows for multiple light reflections, maximizing light absorption, while the exterior shell and inner surfaces simultaneously offer active sites for reactions. The modification with non-noble metal NiS enables the extraction of electrons from CdS to the NiS surface, achieving rapid charge separation. Furthermore, adsorption-free energy calculations reveal that the NiS surface is more conducive to photocatalytic hydrogen generation, providing additional reaction active sites. The results demonstrate a hydrogen production rate of 2.18 mmol g–1 h–1 for CdS/NiS HNS, which is 9.48 times greater than that of pristine CdS. This work presents a novel approach for synthesizing seamlessly interfaced contacts between photocatalysts and cocatalysts, offering new insight into efficient one-step synthesis for enhanced photocatalytic performance.

Porphyrin-based frameworks and derivatives for the oxygen reduction reaction

The global energy crisis and environmental pollution issues caused by the continuous consumption of fossil fuels are increasingly becoming severe. Developing clean and sustainable hydrogen (H2) energy and corresponding storage and conversion devices have attracted increasing attention. The utilization of H2 energy highly depends on the fuel cell (FC). However, the slow kinetics of oxygen reduction reaction (ORR) on the cathode of FC cannot be improved without efficient catalysts. Currently, precious metal platinum (Pt) and its alloys are commonly used catalysts for ORR process. However, the scarcity and high cost of Pt hinder their large-scale practical application. To replace typical Pt-based catalysts, non-precious metal electrocatalysts have been investigated for ORR. Inspired by the catalytic ORR active center Fe porphyrin of cytochrome c oxidase in nature, metalloporphyrin-based frameworks and their derivatives have become promising electrocatalysts due to their abundant conjugated electronic structure, tunable functional groups, and large specific surface area. First, this review briefly introduces porphyrins and catalytic ORR mechanisms. Second, recent progress on porphyrin-based ORR catalysts including porphyrin-based frameworks, framework@substrate composites, and framework-based derivatives was summarized. Porphyrin-based frameworks mainly include metal-organic frameworks (MOFs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and polymers constructed with porphyrin building blocks. Porphyrin-based framework@substrate composites were usually assembled and constructed to improve the electron transfer rate of frameworks. To further improve the conductivity, framework-based derivatives, usually named metal, nitrogen-doped carbon (M-N-C) materials, were synthesized through pyrolyzing frameworks at high temperatures. Finally, research challenges and directions of porphyrin-based electrocatalysts for ORR were discussed. This review is meaningful and enlightening for designing and developing other porphyrin-based electrocatalysts for ORR.

Light-induced in-situ transformation from MOF to construct heterostructured Co3O4/Co catalyst for efficient photothermal catalytic oxidation

The construction of hybrid nanocatalysts with enhanced active surfaces/interfaces is crucial for the catalytic oxidative removal of volatile organic compounds (VOCs). In this study, we report an in-situ conversion approach to synthesize a heterostructured Co3O4/Co catalyst (Co@NC-0.5) for efficient photothermal catalytic oxidation of acetone. The catalysts were prepared by pyrolyzing a mixture of ZIF-67 and melamine. The exposed cobalt species underwent in-situ oxidation to form a Co3O4/Co heterostructure under photothermal conditions. This unique catalyst structure exhibited over 90 % conversion within 16 min under full solar spectrum irradiation and excellent reusability with continuous maintenance of 100 % acetone conversion rate after nine cycles performance tests. Notably, its specific mass activity under thermocatalytic conditions was 2.13 times higher than that of Co3O4. Our work provides a facile and effective strategy for developing highly active and durable non-precious metal catalysts suitable for various photothermal catalytic reactions.

Efficient preparation of carbon materials composed of warped graphene layers via in-situ nano-templating and estimation of oxygen reduction reaction activity

The warped graphene layer (WGL) has garnered attention as a potential alternative to Pt for oxygen reduction reaction (ORR) catalysts and as a platform for enhancing the activity of Pt or molecular catalysts through interactions. We propose an in-situ nano-templating method for the preparation and mass production of WGLs and demonstrate its efficiency. The in-situ nano-templating method facilitates the synthesis of materials with three-dimensional curvature by concurrently generating nanoparticles and carbonizing. The synthesized WGLs exhibited high ORR activity in acidic conditions. Although the ORR activity was not correlated with the surface area, it was strongly correlated with the curvature radius of the WGLs. This activity was considered to arise owing to the optimization of oxygen adsorption ΔG0 with the decrease in the curvature radius of the WGLs; furthermore, the physicochemical characteristics of WGL possesses continuity of carbon layers and exhibit a Fermi level higher than the O2/H2O reduction potential. This report elucidates experimentally that WGLs contribute to ORR activity, suggesting the importance of incorporating WGLs in the development of non-precious metal catalysts.

A versatile non-precious metal based electrode material endowed by layer-on-layer structure for methanol oxidation and supercapacitor applications

A high-performance non-noble metal-based electrode is the need of the hour to resolve the challenge of huge energy demand. Energy conversion and storage devices are the two ways to tackle this challenge. In this context, porous and non-noble metal-based electrodes NiCo2O4 (NCO), NiCo2O4/NiO (CNO) and NiCo2O4/NiO/rGO (CNOG) are developed as a bifunctional electrode for supercapacitor and methanol fuel cell applications. The binary composite of NiCo2O4 with NiO increases the redox sites and enhances its electrochemical activity. The low conductivity and problem of aggregation of transition metal oxides are overcome by developing a hybrid nanocomposite of NiCo2O4/NiO with reduced graphene oxide (rGO). The layer-on-layer morphology of CNOG, and the interfacial interactions among NiCo2O4 nanoflakes, NiO nanoparticles and rGO nanosheets increase the specific surface area of the hybrid, which leads to enhanced ion penetration into the active sites. CNOG acts as a potential anode catalyst for methanol oxidation with excellent structural stability. It exhibits a high methanol oxidation current density with low onset potential and faster kinetics. Symmetric supercapacitor CNOG//CNOG delivers specific capacitance of 59.4989 F/g, energy and power density of 6.69 Wh/kg and 698 W/kg respectively at 3 M KOH aqueous electrolyte. The solid-state symmetric supercapacitor (SSSC) using PVA/KOH electrolyte allows broader potential window, thereby outperforming the aqueous electrolyte. The SSSC exhibits specific capacitance of 88.8 F/g, energy and power density 20.84 Wh/kg and 1003 W/kg respectively at the same current density.

ZIF67-ZIF8@MFC-Derived Co-Zn/NC Interconnected Frameworks Combined with Perfluorosulfonic Acid Polymer as a Highly Efficient and Stable Composite Electrocatalyst for Oxygen Reduction Reactions.

The development of precious metal-free (M-N-C) catalysts for the oxygen reduction reaction (ORR) is considered crucial for reducing fuel cell costs. Herein, Co-Zn/NC interconnected frameworks with uniformly dispersed Co nanoparticles and graphitic carbon are designed and successfully synthesized through the in situ growth of zeolitic imidazolate frameworks (ZIF67 and ZIF8) along with biomass nano-microfibrillar cellulose (MFC), followed by pyrolysis. A Co-Zn/NC composite is prepared by combining Co-Zn/NC with a perfluorosulfonic acid polymer. The Co-Zn/NC composite catalyst exhibits excellent ORR catalytic activity (E0 = 0.974 V vs. RHE, E1/2 = 0.858 V vs. RHE) and good long-term durability, with 90% current retention after 10000s, surpassing that of commercial Pt/C in alkaline media. The hierarchical porous structure, coupled with the uniform distribution of Co nanoparticles and nitrogen doping, contributes to superior electrocatalytic performance, while the interconnected frameworks and graphitic carbon ensure good stability. Additionally, the Co-Zn/NC composite demonstrates promising applications in acidic media. This strategy offers significant guidance to develop advanced non-precious metal carbon-based catalysts for highly efficient and stable ORR.

Carbon-coated Fe3O4@cotton fiber biomass carbon for the oxygen reduction reaction in air cathode microbial fuel cells

Iron-based oxide catalysts on biomass carbon fibers can jointly use their respective advantages of chemical composition and structure to develop catalysts for the oxygen reduction reaction (ORR). In this study, carbon-coated Fe3O4@cotton fiber biomass carbon (C@Fe3O4@CFBC) was prepared as an ORR catalyst through hydrothermal growth and calcination treatment for air cathode microbial fuel cells (MFCs). The carbon coating layer enhanced the O2 adsorption energy, decreased the overpotential, and promoted surface activation of the Fe3O4 catalyst. The carbon coating layer can modulate the surface electronic structure of the Fe3O4 catalyst with C–O–Fe bonding and improve the electrical conductivity to accumulate electrons on the Fe3O4 surface to enhance the ORR performance. The CFBC supported Fe3O4 nanoparticles to prevent severe aggregation and expose more effective surface-active sites. The C@Fe3O4@CFBC catalyst achieved a high positive half-wave potential (0.801 V) and low Tafel slope (73.7 mV·dec−1) compared with the Pt/C catalyst (0.877 V and 94.3 mV·dec−1). The assembled air cathode MFCs achieved a desirable maximum power density (1059 ± 16 mW·m−2) based on 1266 ± 94 mW·m−2 of Pt/C MFC devices. This work provides a strategy for designing highly active non-precious metal catalysts for air cathode MFCs.

Alleviating OH Blockage on the Catalyst Surface by the Puncture Effect of Single-Atom Sites to Boost Alkaline Water Electrolysis.

Nonprecious transition metal catalysts have emerged as the preferred choice for industrial alkaline water electrolysis due to their cost-effectiveness. However, their overstrong binding energy to adsorbed OH often results in the blockage of active sites, particularly in the cathodic hydrogen evolution reaction. Herein, we found that single-atom sites exhibit a puncture effect to effectively alleviate OH blockades, thereby significantly enhancing the alkaline hydrogen evolution reaction (HER) performance. Typically, after anchoring single Ru atoms onto tungsten carbides, the overpotential at 10 mA·cm-2 is reduced by more than 130 mV (159 vs 21 mV). Also, the mass activity is increased 16-fold over commercial Pt/C (MA100 = 17.3 A·mgRu-1 vs 1.1 A·mgPt-1, Pt/C). More importantly, such electrocatalyst-based alkaline anion-exchange membrane water electrolyzers can exhibit an ultralow potential (1.79 Vcell) and high stability at an industrial current density of 1.0 A·cm-2. Density functional theory (DFT) calculations reveal that the isolated Ru sites could weaken the surrounding local OH binding energy, thus puncturing OH blockage and constructing bifunctional interfaces between Ru atoms and the support to accelerate water dissociation. Our findings exhibit generality to other transition metal catalysts (such as Mo) and contribute to the advancement of industrial-scale alkaline water electrolysis.

G-C3N4 modified with non-precious metal Al with LSPR as an efficient visible light catalyst.

The issue of water pollution has emerged as a formidable challenge, prompting a pressing need for solutions. The utilization of metal nanoparticles with surface plasmon resonance and semiconductor composite photocatalysts is regarded as a highly effective approach to solve this problem. g-C3N4 is an effective catalyst for the degradation of organic pollutants. Its photocatalytic performance is usually enhanced by the use of the noble metal Au Ag. However, the high cost of these materials limits their application. In this study, we present the synthesis of Al NPs/g-C3N4 nanocomposites using the bridging effect of ligands. The characterized of transmission electron microscopy (TEM), X-ray diffractometer (XRD) and ultraviolet-visible spectroscopy (UV-Vis) proved that Al NPs/g-C3N4 with a wider light absorption range were successfully synthesized. The effects of ligands, (glutathione (GSH), glutamic acid (GAG), and cysteine (CYS)), Al diameter (40 to 200 nm) and the ratio of Al to g-C3N4 (1:1 to 5:1) on the photocatalytic degradation of methylene blue (MB) by Al NPs/g-C3N4 were also evaluated. The results showed that the optimum degradation efficiency of Al NPs/g-C3N4 for MB at 5 mg/L reached 100% within 60 min, which was 11 times higher than that of pure g-C3N4. The principal analysis of Al enhancing the photocatalytic performance of g-C3N4 was studied through transient photocurrent spectroscopy (TPC), electrochemical impedance spectroscopy (EIS), and steady-state transient fluorescence spectroscopy (PL). The results confirmed that hot carriers generated by localized surface plasmon resonance (LSPR) of Al nanoparticles increase the carrier concentration. In addition, the Schottky barrier generated by Al and g-C3N4 could also improve the carrier separation rate and increase the carrier lifetime. This work is expected to solve the problem of organic wastewater treatment and lay the foundation for subsequent research on photocatalysis.

NiCoP cocatalyst modified g-C3N4 as ohmic junction photocatalyst for efficient degradation of tetracycline under visible light

Increasing the electron-hole recombination rate in g-C3N4 can effectively improve its photocatalytic performance. In this work, NiCoP/g-C3N4 (NCP/PCN) composites with ohmic junction were formed by embedding granular NiCoP in irregularly porous g-C3N4. There was almost no barrier between the metal and the semiconductor in ohmic junction, which made it easier for electrons to slip from PCN to NCP along the curved energy band, and NCP acted as an electron collector to rapidly capture the slipping electrons. In addition, porous g-C3N4 prepared by supramolecular self-assembly could provide a shorter diffusion path for electrons. Thus, the electron-hole was effectively separated and the photocatalytic performance was improved. The band electronic structure and existence of ohmic junction in 7-NCP/PCN composite were demonstrated by XPS, ESR and DFT calculation. Finally, a reasonable photocatalytic degradation mechanism and possible tetracycline degradation path were proposed. This work has significant potential for providing an effective method for the design of non-precious metal photocatalysts.

Study on electrochemical properties of Pt-Ni nanocatalysts with high index crystal facets

We prepared Pt-Ni high-index crystalline nanoparticles with various Pt-Ni molar ratios to study the microscopic morphology and electrochemical properties of these catalysts. The results demonstrated that when Pt: Ni is 1:1, the prepared catalyst has the most uniform morphology and the optimal catalytic activity, as evidenced by an electrochemical active area of 8.546 m2/g, the current density of 1.544 mA/cm2 for ethanol oxide and 1100 s steady state current density of 1.132 mA/cm2. Pt-Ni high-index crystalline nanocatalysts have such high catalytic efficiencies due to the abundance of step atoms and the doping of non-precious metal nickel.

Oxalic Acid-Assisted Vacancy Engineering Promotes Iron-Copper Sulfide Nanosheets for High-Current Density Water Oxidation.

The effective defect and interface coupling are pivotal for the promotion of the catalytic activity for the oxygen evolution reaction. Herein, we report novel hybrid nanosheets with sulfur vacancies composed of FeS2 and Cu39S28 grown on Cu foam (Vs-FeS2/Cu39S28). The optimal Vs-FeS2/Cu39S28 exhibits a high current output of 500 mA cm-2 at a low overpotential of 370 mV and robust stability for 60 h at 100 mA cm-2, surpassing the values of most previously reported Cu-based catalysts. Furthermore, a two-electrode electrolyzer made by pairing the prepared catalyst with commercial Pt/C requires a low cell voltage of 1.75 V at 100 mA cm-2 and is retained over 80 h. Key to its excellent performance is the synergism between intertwined FeS2 and Cu39S28 domains, enriched by the deliberate introduction of sulfur vacancies, thus optimizing the electronic structure and causing the proliferation of catalytic active sites. This work presents a potent Cu-based electrocatalyst and emphasizes the leveraging of non-precious metals for efficient water oxidation.

Capacitance Determination for the Evaluation of Electrochemically Active Surface Area in a Catalyst Layer of NiFe-Layered Double Hydroxides for Anion Exchange Membrane Water Electrolyser.

The determination of the electrochemically active surface area (ECSA) of a catalyst layer (CL) of a non-precious metal catalyst is of fundamental importance in optimizing the design of a durable CL for anion exchange membrane (AEM) water electrolysis, but has yet to be developed. Traditional double layer capacitance (Cdl), measured by cyclic voltammetry (CV), is not suitable for the estimation of the ECSA due to the nonconductive nature of Ni-based oxides and hydroxides in the non-Faradaic region. This paper analyses the applicability of electrochemical impedance spectroscopy (EIS) compared to CV in determining capacitances for the estimation of the ECSA of AEM-based CLs in an aqueous KOH electrolyte solution. A porous electrode transmission line (TML) model was employed to obtain the capacitance-voltage dependence from 1.0 V to 1.5 V at 20 mV intervals, covering both non-Faradic and Faradic regions. This allows for the identification of the contribution of a NiFe-layered double hydroxide (LDH) catalyst and supports in a CL, to capacitances in both non-Faradic and Faradic regions. A nearly constant double layer capacitance (Qdl) observed in the non-Faradic region represents the interfaces between catalyst supports and electrolytes. The capacitance determined in the Faradic region by EIS experiences a peak capacitance (QF), which represents the maximum achievable ECSA in an AEMCL during reactions. The EIS method was additionally validated in durability testing. An approximate 30% loss of QF was noted while Qdl remained unchanged following an eight-week test at 1 A/cm2 constant current density, implying that QF, determined by EIS, is sensitive to and therefore suitable for assessing the loss of ECSA. This universal method can provide a reasonable estimate of catalyst utilization and enable the monitoring of catalyst degradation in CLs, in particular in liquid alkaline electrolyte water electrolysis systems.