Stable Electrocatalysts Research Articles

Terbium- and samarium-doped Li2ZrO3 perovskite materials as efficient and stable electrocatalysts for alkaline hydrogen evolution reactions

The preparation of highly active, rare earth, non-platinum-based catalysts for hydrogen evolution reactions (HER) in alkaline solutions would be useful in realizing green hydrogen production technology. Perovskite oxides are generally regarded as low-active HER catalysts, owing to their unsuitable hydrogen adsorption and water dissociation. In this article, we report on the synthesis of Li2ZrO3 perovskites substituted with samarium and terbium cations at A-sites for the HER. LSmZrO3 (LSmZO) and LTbZrO3 (LTbZO) perovskite oxides are more affordable materials, starting materials in abundance, environmentally friendly due to reduced usage of precious metal and moreover have potential for several sustainable synthesis methods compared to commercial Pt/C. The surface and elemental composition of the prepared materials have been confirmed by X-ray photoelectron spectroscopy (XPS). The morphology and composition analyses of the LSmZO and LTbZO catalysts showed spherical and regular particles, respectively. The electrochemical measurements were used to study the catalytic performance of the prepared catalyst for hydrogen evolution reactions in an alkaline solution. LTbZO generated 2.52 mmol/g/h hydrogen, whereas LSmZO produced 3.34 mmol/g/h hydrogen using chronoamperometry. This was supported by the fact that the HER electrocatalysts exhibited a Tafel slope of less than 120 mV/dec in a 1.0 M alkaline solution. A current density of 10 mA/cm2 is achieved at a potential of less than 505 mV. The hydrogen production rate of LTbZO was only 58.55%, whereas LSmZO had a higher Faradaic efficiency of 97.65%. The EIS results demonstrated that HER was highly beneficial to both electrocatalysts due to the relatively small charge transfer resistance and higher capacitance values.

Spider silk inspired ultrafine carbon nanotubes-crosslinked porous carbon fibers for Zn-air batteries

There is a critical need for the development of low-cost, highly efficient, and stable bifunctional oxygen electrocatalysts for the advancement of Zn-air battery (ZAB). This study presents an Fe-, Ni-, and N-co-doped porous carbon material (FeNiN-CF-15) synthesized through the pyrolysis of a mixture combining the melamine and electrospun fibers. This material comprises carbon fiber substrates and spider silk-like ultrafine carbon nanotubes (CNTs) catalytically grown from FeNi alloys. With a high N doping level (12.9 at%), large specific surface area (385.18 m2 g−1), and conductive carbon network composed of CNTs, the new electrocatalyst exhibits outstanding bifunctional oxygen electrocatalytic performances. Specifically, it achieves a half-wave potential of 0.853 V for oxygen reduction reaction (ORR) and 1.571 V for oxygen evolution reaction (OER) at 10 mA cm−2. The exceptional ORR/OER electrocatalytic activity enables the FeNiN-CF-15-based liquid ZAB to deliver a high initial energy efficiency of 62.12 %, narrow charging/discharging voltage gap of 0.742 V, and robust cycling stability within 960 cycles for 320 h at 5 mA cm−2. Additionally, the reported electrocatalyst is proven competent for use in a flexible ZAB.

Microwave-edge-thermal effect induced growth of coral-like self-supporting CoFe2O4/NF electrocatalysts for efficient water splitting at high-current–density

High-efficiency and long-term water-splitting to produce hydrogen under the high-current–density (HCD) environment is a severe challenge because the swift-consumption of electrolyte and large-production of bubbles require better charge/mass-transfer capability and durability of electrocatalysts. Rationally design and effectively construct of three-dimensional (3D) hierarchical electrocatalysts is the promising solutions to accelerate the charge/mass transfer rates during water splitting process. Herein, a 3D self-supporting coral-like oxygen evolution reaction (OER) electrode was synthesized using a microwave-edge-thermal (MET) effect induced heterogeneous-nucleation/oriented-attachment growth process by in-situ growing CoFe2O4 nanocrystals on nickel-foams (CoFe2O4/NF). SEM, TEM, electrolyte/catalyst contact angles, in-situ observation of O2 bubbles generation-evolution process, and three-electrode configuration (TEC) and anion-exchange-membrane (AEM) electrocatalytic OER tests at the HCD were used to investigated the structure–activity relationship of the CoFe2O4/NF electrode. The CoFe2O4/NF electrode offered super hydrophilic/aerophobic surfaces and firmly bonded interfaces, resulting in quicker charge/mass-transfer rates and long-term durability under the HCD conditions. The typical electrode exhibited a low OER overpotential of 0.24 V at 10 mA cm−2 and a Tafel slope of 35.2 mV dec−1; its alkaline AEM electrolyzer (Pt || CoFe2O4/NF) yielded a HCD of 1200 mA cm−2 at only 2.36 V and 60˚C and kept stable over 120 h. This work provides a new insight into the design and fabrication of active and stable non-noble metal-based OER electrocatalysts for cost-effective water-electrolysis applications.

Nanoarchitectonics of few-layer Ni3Fe nanosheets embedded porous nitrogen-doped carbon derived from asphalt waste: An efficient electrocatalyst for oxygen evolution reaction

The design and fabrication of stable, high-performance, and affordable oxygen evolution reaction (OER) electrocatalysts is essential for performing practical water electrolysis and generating green hydrogen energy. Here, we report that 2D few layer Ni3Fe nanosheets embedded with 2D porous nitrogen doped carbon (N-NixFe@CF) from asphalt waste and then convolved and assembled into 1D hollow nanotube structures by Lewis acid molten salt etching method, which were used as electrocatalysts for OER. Benefiting from the integrate of 1D hollow nanotube structure and 2D porous nanosheets, the close contact between catalysts and support, and the increased conductivity, the resultant N-Ni3Fe@CF catalysts exhibited high catalytic activities in the OER with low overpotential at a current density of 10 mA cm−2 (114 mV), low Tafel slope (166.6 mV dec−1), and excellent electrochemical stability. This work provides a new concept for expanding the use of asphalt wastes and by-products, as well as a straightforward synthesis method for producing economical, efficient, and long-lasting alkaline OER electrocatalysts.

Revealing the role of 1T- & 2H- molybdenum Disulfide/Nickel sulfide heterojunction for efficient overall water splitting

In the ongoing quest for cost-effective and durable electrocatalysts for hydrogen production—a critical element of sustainable energy transformation—the 1T phase of Molybdenum Disulfide (MoS2) faces challenges due to its thermodynamic instability and the trade-off between efficiency and durability. Conversely, the 2H phase of MoS2, often disregarded in favor of the metallic 1T phase, suffers from its inert nature and limited active sites. To overcome these limitations, this study employs a straightforward hydrothermal synthesis strategy that couples both 1T and 2H phases of MoS2 with Ni3S2, forming 1T- and 2H- MoS2/Ni3S2 heterojunctions. Enhanced by Ni3S2′s abundant active sites, improved electron transport capabilities, synergistic interface effects, and better structural stability, these heterojunctions achieve a high current density exceeding 500 mA cm−2 at low overpotentials, along with prolonged durability for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline electrolytes. Remarkably, an electrolyzer assembly utilizing 1T-MoS2/Ni3S2 as the cathode and 2H-MoS2/Ni3S2 as the anode demonstrates a competitive voltage of 1.58 V at 20 mA cm−2, showcasing superior performance in overall water splitting compared to other non-noble metal-based electrocatalysts. This study not only offers a viable method for synthesizing efficient and stable electrocatalysts for water splitting using transition metal-based heterogeneous structures but also addresses the fundamental challenges associated with 1T and 2H phases of MoS2.

Scaling Up Stability: Navigating from Lab Insights to Robust Oxygen Evolution Electrocatalysts for Industrial Water Electrolysis

AbstractIn the pursuit of sustainable hydrogen production via water electrolysis, paramount importance of electrocatalyst stability emerges as a defining factor for long‐term industrial viability. A thorough understanding and enhancement of stability not only ensure extended catalyst lifetimes but also pave the way for consistent and efficient hydrogen generation. This review focuses on the pivotal role of stability in determining the practical viability of oxygen evolution electrocatalysts (OECs) for large‐scale applications in water electrolysis for hydrogen production. The paper explores the pivotal role of stability over initial activity, citing examples and hypothetical scenarios. First, figures of merits for stability evaluation of the electrocatalyst are explained along with the available benchmarking protocols for stability evaluation. Further, the text delves into various strategies that can enhance the stability of the electrocatalyst which include self‐healing/regeneration pathway, oxygen evolution reaction (OER) mechanism optimization to achieve highly stable OER and stabilization of active metals atoms within the electrocatalyst to inhibit dissolution as a way forward for industrial application. The interplay of stability, activity, and cost is also explained to suit the industrial application of the electrocatalyst. Lastly, it outlines challenges, prospects, and future directions, presenting a guide for advancing OECs in the hydrogen generation landscape.

Factors influencing the stability of Pt-based ORR electrocatalysts in HT-PEMFCs: A theoretical investigation

Electrocatalyst stability is a key parameter for commercializing high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Here, we used density functional theory (DFT) to investigate the stability of Pt-based electrocatalysts by calculating the binding energy (ΔEb) of surface Pt atoms under working conditions. Our results show that Pt(111) is more stable than Pt(100) and Pt(110) under vacuum conditions. Stress hurts the stability of Pt(111), regardless of compressive or tensile stress. Most of the transition metals alloyed with Pt improve the stability of Pt(111), especially PtV, PtY, and PtTa, which increase the ΔEb by 0.60–0.70 eV (ΔΔEb). However, the stability of Pt is significantly destroyed under the working conditions of oxygen reduction reaction (ORR). The specific adsorption of ORR intermediates and electrolyte ions decreases the ΔEb of Pt(111) by 0.35–0.95 eV, and the effect of PO43-* is more significant. Furthermore, when the electric field of the electrochemical double layer is coupled with PO43-* specific adsorption, ΔΔEb further increases to 1.12 eV. Our results highlight the importance of the intrinsic ΔEb and the working conditions for the stability of Pt-based electrocatalysts. This work provides important guidelines for the design of stable ORR electrocatalysts for HT-PEMFCs.

Metal–Organic Frameworks as a Catalyst and Catalyst Support in Fuel Cells: From Challenges to Catalytic Application

AbstractThe innovation of high‐performance, stable electrocatalysts for clean energy systems faces significant challenges. Metal‐organic frameworks (MOFs), with their porous nature, flexible structures, and homogeneous active site dispersion, have gained interest as unique precursors for carbon‐based catalysts. MOFs' properties significantly enhance catalytic performance in fuel cells. This review highlights recent advancements in MOF design for oxygen electrocatalysis in fuel cells, while also discussing perspectives for future material innovations to improve catalytic activity in this emerging field.

Physical insight into the enhanced urea electrooxidation using Ni and Fe-based LDH, LDO, and hydroxides under different dissolved gas saturation conditions in electrolyte

The production of green hydrogen is one of the most demanding and challenging for modern technology. A promising and an effective approach is electrocatalytic anodic urea oxidation reaction to generate hydrogen at cathode under alkaline electrolysis condition. However, it remains crucial for the development of active and stable electrocatalysts for efficient urea oxidation. In this study, we employed the hydrothermal synthesis route for NiFe LDH, NiFe LDO, and Ni(OH)2. The superior performance of NiFe LDH compared to other catalysts is observed due to easy charge transfer facilitated by Fe ions. Moreover, Fe incorporation prevents surface poisoning of the electrocatalyst, resulting in increased activity and stability for electrocatalytic urea oxidation reaction. The influence of different electrolyte environments on the performance of urea-based electrolyzers for sustainable hydrogen production and management of urea-rich wastewater has been measured for the first time by varying oxygen saturation and nitrogen purging conditions. In cyclic voltammetry studies, O2-saturated and purging conditions outperformed N2 gas saturation or purging. The findings of this study provide valuable insight into the design of practical and environmentally friendly urea electrooxidation systems.

Engineered CoS/Ni3S2 Heterointerface Catalysts Grown Directly on Carbon Paper as an Efficient Electrocatalyst for Urea Oxidation

Developing highly efficient and stable electrocatalysts for urea electro-oxidation reactions (UORs) will improve wastewater treatment and energy conversion. A low-cost cobalt sulfide-anchored nickel sulfide electrode (CoS/Ni3S2@CP) was synthesized by electrodeposition in DMSO solutions and found to be highly effective and long-lasting. The morphology and composition of catalyst surfaces were examined using comprehensive physicochemical and electrochemical characterization. Specifically, CoS/Ni3S2@CP electrodes require a potential of 1.52 volts for a 50 mA/cm2 current, confirming CoS in the heterointerface CoS/Ni3S2@CP catalyst. Further, the optimized CoS/Ni3S2@CP catalyst shows a decrease of 100 mV in the onset potential (1.32 VRHE) for UORs compared to bare Ni3S2@CP catalysts (1.42 VRHE), demonstrating much greater performance of UORs. As compared to Ni3S2@CP, CoS/Ni3S2@CP exhibits twofold greater UOR efficiency as a result of a larger electroactive surface area. The results obtained indicate that the synthetic CoS/Ni3S2@CP catalyst may be a favorable electrode material for managing urea-rich wastewater and generating H2.

Electrocatalytic ammonia synthesis on bimetallic AuPd porous structures

In industry, production of ammonia mainly relies on the intensive Haber-Bosch process, but it consumes high energy with low efficiency and generates a large number of green-house gases. Electrocatalytic nitrogen reduction reaction (ENRR), as an alternative method for fixing N2 under ambient conditions, provides a feasible strategy for sustainable development of N2 cycle storage and utilization of renewable energy. However, traditional nanocatalysts exhibit extremely poor ENRR performance due to low activity of the solid structure and intense hydrogen evolution reactions of single component. Herein, we design and prepare porous gold–palladium nanoalloys (pAuPdNs), which effectively enhance ENRR by the excellent catalytic activity of Au and the significant N2 fixation ability of Pd, as well as the nanoporous structure and synergistic effect between alloy components. The electrochemical results show the NH3 yield of the catalyst is as high as 43.6 μg·h−1·cm−2, and Faradaic efficiency reaches 43.8%, which are superior to the performances of most reported water-based ENRR electrocatalysts. Besides, the selectivity of 95% and stability also exhibit enhancement than numerous reported researches. As compared with solid alloy and porous Au or Pd structures, the superiority of pAuPdNs states the influence of alloying and porous structure. Hence pAuPdNs are proved to be the efficient, stable, and promising electrocatalysts for N2 reduction reaction at ambient temperature and atmospheric pressure.

Chemical Epitaxy of Iridium Oxide on Tin Oxide Enhances Stability of Supported OER Catalyst.

Significantly reducing the iridium content in oxygen evolution reaction (OER) catalysts while maintaining high electrocatalytic activity and stability is a key priority in the development of large-scale proton exchange membrane (PEM) electrolyzers. In practical catalysts, this is usually achieved by depositing thin layers of iridium oxide on a dimensionally stable metal oxide support material that reduces the volumetric packing density of iridium in the electrode assembly. By comparing two support materials with different structure types, it is shown that the chemical nature of the metal oxide support can have a strong influence on the crystallization of the iridium oxide phase and the direction of crystal growth. Epitaxial growth of crystalline IrO2 is achieved on the isostructural support material SnO2, both of which have a rutile structure with very similar lattice constants. Crystallization of amorphous IrOx on an SnO2 substrate results in interconnected, ultrasmall IrO2 crystallites that grow along the surface and are firmly anchored to the substrate. Thereby, the IrO2 phase enables excellent conductivity and remarkable stability of the catalyst at higher overpotentials and current densities at a very low Ir content of only 14 at%. The chemical epitaxy described here opens new horizons for the optimization of conductivity, activity and stability of electrocatalysts and the development of other epitaxial materials systems.

Ultrathin Carbon Shell Protecting Copper Sites to Boost Anodic Hydrogen Production via Low-Potential Formaldehyde Oxidation.

The oxidation of aldehydes on a copper-based electrocatalyst within a small potential window can produce hydrogen at the anode, thus offering a bipolar hydrogen production system. However, the inherent activity and stability of Cu-based electrocatalysts for aldehyde oxidation are still not satisfactory in practical application. Herein, by coating an ultrathin carbon shell on the copper sphere, an effective and stable formaldehyde oxidation reaction (FOR) can be realized to produce H2 at a very low potential. FOR needs only a potential of 0.13 V (vs RHE) to reach a current density of 100 mA cm-2. By coupling FOR with hydrogen evolution reaction (HER), hydrogen is generated simultaneously at both the cathode and the anode. The Faraday efficiency of H2 at the bipolar state is close to 100%. In a flow cell, it needs a low cell voltage of 0.1 V to reach a current density of 100 mA cm-2. Moreover, it can be operated steadily for more than 30 h at high current density. The carbon shell acts as an armor to protect the Cu(0) sites, avoid the oxidation of copper, and keep the catalyst activity for a long time in the electrolytic process. Experimental and theoretical calculation results indicate that electron transfer occurs at the interface between the copper core and ultrathin carbon shell. The ultrathin carbon-coated Cu reduces the reaction energy barrier, making the C-H bond more easily fractured and facilitating H coupling to generate H2. This study provides a basic principle for the design of copper-based electrocatalysts with long durability and activity.

Phosphate-decorated hierarchical porous CoNiFe medium-entropy alloy: An efficient and low-cost electrocatalyst for seawater oxidation

The development of efficient, stable and low-cost electrocatalysts towards the seawater oxidation is highly desirable for hydrogen-based industries. In this work, we report the efficient preparation of phosphate-decorated hierarchical porous CoNiFe medium-entropy alloys as promising electrocatalysts for the oxygen evolution reaction in seawater via the solution combustion synthesis. The hierarchical porous structure of CoNiFe medium-entropy alloys enhances exposure to catalytic sites and facilitates the efficient diffusion of gas products as well as electrolytes. Moreover, the in-situ formed PO43− anions not only improve the electrocatalytic performance of CoNiFe medium-entropy alloys for oxygen evolution reaction, but also prevent Cl− from contacting the catalytic sites. Thanks to these structural benefits, the optimized CoNiFeP0.1@NF electrode demonstrates superior electrocatalytic performance for oxygen evolution reaction, showing an overpotential of 250 mV at 10 mA cm−2, a low Tafel slope of 47.6 mV dec−1, and satisfactory stability in the 1.0 M KOH +0.5 M NaCl electrolyte.

Graphitized carbon-anchored FeSe nanoparticles for stable and efficient bifunctional electrocatalyst in rechargeable zinc-air batteries

Developing zinc-air batteries still heavily relies on the design of stable, high-activity, and inexpensive oxygen-electric bifunctional catalysts. In this work, transition metal iron salts converted amorphous carbon into graphitized carbon at high temperatures, and nitrogen-doped graphitized carbon-anchored iron nanoparticles (Fe–N–C) are prepared. Then, Fe–N–C is pyrolyzed with selenium dioxide (SeO2) to convert iron (Fe) nanoparticles into iron selenide (FeSe) in situ to obtain nitrogen-doped graphitized carbon-anchored FeSe nanoparticle catalysts (FeSe/NC). The catalyst's carbon support has excellent electrical conductivity, which effectively promotes the transport rate of charges and enhances the catalytic activity of FeSe particles. FeSe/NC demonstrates outstanding catalytic activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). When utilizing FeSe/NC catalysts in rechargeable zinc-air batteries (ZABs-FeSe/NC), the most excellent power density could exceed 186.6 mW cm−2, and the specific capacity can achieve 905.2 mAh g−1, demonstrating excellent performance. Furthermore, the battery can achieve stable charge-discharge for longer than 200 h at a large current density of 10 mA cm−2, which has excellent practical application feasibility in the future.

Accelerating the design of catalysts for CO2 electroreduction to HCOOH: A data-driven DFT-ML screening of dual atom catalysts

Dual-atom catalysts (DACs) have emerged as potential catalysts for effective electroreduction of CO2 due to their high atom utilization efficiency and multiple active sites. However, the screening of DACs remains a challenge due to the large number of possible combinations, making exhaustive experimental or computational screening a daunting task. In this study, a density functional theory (DFT)-based machine learning (ML)-accelerated (DFT-ML) hybrid approach was developed to test a set of 406 dual transition metal catalysts on N-doped graphene (NG) for the electroreduction of CO2 to HCOOH. The results showed that the ML algorithms can successfully capture the relationship between the descriptors of the DACs (inputs) and the limiting potential for HCOOH generation (output). Of the four ML algorithms studied in this work, the feedforward neural network model achieved the highest prediction accuracy (the highest correlation coefficient (R2) of 0.960 and the lowest root mean square error (RMSE) of 0.319 eV on the test set) and the predicted results were verified by DFT calculations with an average absolute error of 0.14 eV. The DFT-ML approach identified Co-Co-NG and Ir-Fe-NG as the most active and stable electrocatalysts for the electrochemical reduction of CO2 to HCOOH. The DFT-ML hybrid approach exhibits exceptional prediction accuracy while enabling a significant reduction in screening time by an impressive 64% compared to conventional DFT-only calculations. These results demonstrate the immense potential of using ML methods to accelerate the screening and rational design of efficient catalysts for various energy and environmental applications.

Molecular O2 Dimers and Lattice Instability in a Perovskite Electrocatalyst.

Structural degradation of oxide electrodes during the electrocatalytic oxygen evolution reaction (OER) is a major challenge in water electrolysis. Although the OER is known to induce changes in the surface layer, little is known about its effect on the bulk of the electrocatalyst and its overall phase stability. Here, we show that under OER conditions, a highly active SrCoO3-x electrocatalyst develops bulk lattice instability, which results in the formation of molecular O2 dimers inside the bulk and nanoscale amorphization induced via chemo-mechanical coupling. Using high-resolution resonant inelastic X-ray scattering and first-principles calculations, we unveil the potential-dependent evolution of lattice oxygen inside the perovskite and demonstrate that O2 dimers are stable in a densely packed crystal lattice, thus challenging the assumption that O2 dimers require sufficient interatomic spacing. We also show that the energy cost of local atomic rearrangements in SrCoO3-x becomes very low under the OER conditions, leading to an unusual amorphization under intercalation-induced stress. As a result, we propose that the amorphization energy can be calculated from the first principles and can be used to assess the stability of electrocatalysts. Our study demonstrates that extreme oxidation of electrocatalysts under OER can intrinsically destabilize the lattice and result in bulk anion redox and disorder, suggesting why some oxide materials are unstable and develop a thick amorphous layer under water electrolysis conditions.

M (M=Mn, Fe, and Cu)-doped Ni3S2@Co9S8 grown on Ni foam with different heterostructures as catalysts for overall seawater splitting

The increasing global energy demand and the environmental impact of fossil fuels have prompted scientists to seek clean and renewable energy solutions. Hydrogen energy, known for its efficiency and environmental benefits, is considered an ideal choice. Given the limited availability of freshwater resources, this study uses abundant seawater as the feedstock for water electrolysis. Our research focuses on developing non-precious metal electrocatalysts to enhance the efficiency and economic viability of water electrolysis for hydrogen production. Using Ni3S2@Co9S8 as the base material, we regulate the catalytic performance by doping with transition metals such as Mn, Fe, and Cu. The Mn-Ni3S2@Co9S8/NF electrode exhibits excellent hydrogen evolution reaction (HER) (overpotential of 76 mV @10 mA cm−2) and oxygen evolution reaction (OER) (overpotential of 261 mV @10 mA cm−2) activity in seawater electrolytes, significantly reducing the overpotential requirements. Density Functional Theory (DFT) assessments reveal that Co9S8 possesses optimal gibbs free energy capabilities and Mn-Ni3S2 possesses more electron distribution, explaining its high catalytic efficiency. This study provides an in-depth analysis of the catalyst structure and performance, offering valuable insights for developing efficient and stable electrocatalysts for water electrolysis, thereby contributing to the sustainable development of the hydrogen economy and advancements in clean energy technology.

Electrocatalyst for the oxygen reduction reaction (ORR): towards an active and stable electrocatalyst for low-temperature PEM fuel cell

Electrocatalyst for the oxygen reduction reaction (ORR): towards an active and stable electrocatalyst for low-temperature PEM fuel cell

Enhancement of acidic hydrogen evolution reaction efficiency through Cu/Ni-doped MFI-type protozeolite layered nanoclusters.

We have prepared a highly active and stable copper-doped nickel electrocatalyst. Cu/Ni-doped MFI-type protozeolite layered nanoclusters electrodes have a large electrochemically active surface area (ECSA) and good HER activity, as well as excellent durability. The addition of Cu greatly increases hydrogen evolution reaction (HER) activity under acidic conditions. At the same time, the in situ grown Cu2+1O provides some activity, and in addition, the interface constructed between Cu and Ni further generates sufficient electrochemically active surface area. The activated Cu/Ni-doped MFI-type layered nanoclusters required only a 385 mV overpotential to generate 10 mA cm-2, demonstrating efficient and stable activity with potential practical applications.