Heterostructure Electrocatalyst Research Articles

F-Doped CoFe Bimetallic Heterostructure Electrocatalyst with Ultra-Low Impedance for High-Current-Density Alkaline Hydrogen Evolution.

The electrolysis of water for hydrogen production has gained increasing attention as a sustainable and efficient method to obtain high-purity green hydrogen. The development of efficient catalysts for hydrogen evolution is crucial in order to achieve this target under industrial conditions. The objective of this work is to synthesize a highly efficient F-CoxFey(POn)z/IF catalyst with ultra-low impedance for hydrogen evolution in electrolytic water by incorporating metal phosphatides into metal oxide nanoclusters through a controlled two-step process involving melting and electrodeposition. The nano-heterostructure of F-CoxFey(POn)z/IF exhibits a low overpotential of 276mV at a current density of 1000mA cm-1, while having an electrochemical impedance comparable to commercial Pt/C/CP (0.41 Ω), and long-term stability up to 200h in 1M KOH electrolyte. The synergistic effect of crystal/amorphous heterojunctions, F doping, and oxygen vacancies further enhances the kinetics of water cracking. Impressively, when combined with NiFeCo LDH/NiS/NF as membrane electrodes, F-CoxFey(POn)z/IF || NiFeCo LDH/NiS/NF achieves a water decomposition voltage of 2.03V at a current density of 1000mA cm-2 and demonstrates stable operation for over 500h, showing great potential for large-scale commercial production.

Ternary amorphous/crystalline NiMoB/Ni@Ti3C2 heterostructures with electronic modulation for high-performance alkaline hydrogen evolution catalysis

Constructing multicomponent heterostructures with coexisting amorphous and crystalline phases offers a promising strategy to finely optimize electronic structures and thereby promote the hydrogen evolution reaction (HER) kinetics in alkaline media. Here, we design a ternary heterostructure consisting of amorphous/crystalline NiMoB/Ni anchored on Ti3C2 MXene (denoted as a-NiMoB/c-Ni@Ti3C2), which fully leverages synergistic electronic modulation at the heterointerfaces. This architecture significantly enhances active site exposure, improves charge transfer efficiency, and stabilizes the catalyst framework. As a result, the a-NiMoB/c-Ni@Ti3C2 catalyst achieves an impressive HER performance, requiring an overpotential of only 87.8 mV to deliver 10 mA cm−2 with a low Tafel slope of 40.3 mV dec−1 and excellent operational durability in 1 M KOH. Density functional theory calculations combined with photoelectron spectroscopy analysis reveal that interfacial electronic interactions between NiMoB/Ni and Ti3C2 critically drive the improved HER kinetics. This work offers a perspective for the rational design of high-efficiency ternary heterostructure electrocatalysts for alkaline hydrogen production.

NiCu-based amorphous/crystalline heterostructure electrocatalyst for highly efficient 5-hydroxymethylfurfural upgrading

NiCu-based amorphous/crystalline heterostructure electrocatalyst for highly efficient 5-hydroxymethylfurfural upgrading

Engineering Ru‐Complementary Catalytic Centers on Co2P/CoP Heterojunction for Industrial Alkaline Water Electrolysis

Abstract Advancing industrial‐scale water electrolysis critically hinges on developing ultra‐active and ultra‐durable catalysts. Herein, a novel Ru‐doped Co2P/CoP heterostructure electrocatalyst (Ru‐Co2P/CoP/CF) is fabricated via an in situ self‐derivation strategy. By regulating the spatial distribution of Ru in the Co2P/CoP heterojunction, the coexisting system integrating Ru atomic clusters (AC) and Ru single atoms (SA) is engineered. Further poisoning experiments and DFT calculations reveal that the dual Ru species exhibit complementary catalytic functionalities for the hydrogen/oxygen evolution reactions (HER/OER). The electron‐rich Ru AC improves the H2O‐adsorption and *OH desorption, boosting the Volmer step of the HER process. While the electron‐deficient Ru SA accelerates OER kinetics by promoting O* desorption and weakening *OOH binding. Moreover, the Co2P/CoP heterojunction establishes an electron equilibration channel, which provides adaptive electron supply and antioxidative microenvironment to Ru, mitigating Ru solvation by stabilizing its electronic states. Benefiting from the Ru‐complementary catalytic centers and heterojunction‐driven charge equilibration, Ru‐Co2P/CoP/CF demonstrates top‐level properties and stability in 1.0 M KOH, requiring ultralow overpotentials of 98 mV (HER) and 360 mV (OER) at 1 A cm−2, along with stability of 4000 h. This work overcomes the selectivity dilemma of single‐type Ru sites for HER/OER, and offers a scalable in‐situ self‐derivation strategy for designing high‐efficiency TMPs electrocatalysts.

Dynamic Electron Spring Effect in Hollow Fe2O3/CoSe2 Heterostructure Enhance Ethanol Electro‐Oxidation Activity and Stability

Abstract Developing efficient non‐noble electrocatalysts with high activity and selectivity for ethanol oxidation reaction (EOR) across a wide potential range remains a significant challenge in hybrid energy systems. Herein, hollow Fe2O3/CoSe2 heterostructures (H‐Fe2O3/CoSe2@C) via interface engineering are reported as highly effective EOR promising electrocatalysts. Characterizations reveal that Fe2O3 functions as a dynamic electron spring to tune the electronic structure of Co sites, accelerating the formation of the Fe2O3/CoOOH heterostructure while suppressing Fe2O3/CoO2 evolution. In situ Raman spectroscopy and theoretical calculation confirm that the Fe2O3/CoOOH heterostructure enhances EOR kinetics and lowers the energy barrier of the potential‐determining step. Quasi in situ X‐ray photoelectron spectroscopy further demonstrates that Fe2O3 stabilizes Co3+against overoxidation, expanding the operational potential window. Consequently, H‐Fe2O3/CoSe2@C achieves outstanding EOR performance, exhibiting 10 mA cm−2 @1.30 V vs. RHE with a high faradaic efficiency of 99% at 1.30 V. Ethanol‐assisted Zn‐Air battery/water splitting devices based on H‐Fe2O3/CoSe2@C demonstrate enhanced energy conversion efficiency, with voltage reduced by 210 and 180 mV at 10 mA cm−2, respectively. This work provides critical insights for designing heterostructure electrocatalysts and advancing the utilization of biomass energy.

Constructing NiCo-hydroxide/Ni Mott-Schottky heterostructure electrocatalyst for enhanced alkaline hydrogen evolution reaction by inducing interfacial electron redistribution.

Constructing NiCo-hydroxide/Ni Mott-Schottky heterostructure electrocatalyst for enhanced alkaline hydrogen evolution reaction by inducing interfacial electron redistribution.

Enhanced electrooxidation of 5-hydroxymethylfurfural over a ZIF-67@β-Ni(OH)2/NF heterostructure catalyst: Synergistic effects and mechanistic insights.

Enhanced electrooxidation of 5-hydroxymethylfurfural over a ZIF-67@β-Ni(OH)2/NF heterostructure catalyst: Synergistic effects and mechanistic insights.

Synthesis of highly efficient bifunctional Nd2S3-MoSe2 heterostructure electrocatalyst for overall water-splitting

Synthesis of highly efficient bifunctional Nd2S3-MoSe2 heterostructure electrocatalyst for overall water-splitting

Rational design of transition metal-based heterostructure electrocatalysts for high-performance oxygen evolution reaction

Rational design of transition metal-based heterostructure electrocatalysts for high-performance oxygen evolution reaction

Enhancing hydrogen evolution by heterointerface engineering of Ni/MoN catalysts.

Enhancing hydrogen evolution by heterointerface engineering of Ni/MoN catalysts.

High-entropy heterostructure electrocatalyst with built-in electric field regulation for efficient oxygen evolution reaction

High-entropy heterostructure electrocatalyst with built-in electric field regulation for efficient oxygen evolution reaction

CeF3-Accelerated surface reconstruction of MoO2 nanosheets into coral-like CeF3/MoO2 composites enhances the oxygen evolution reaction for efficient water splitting.

CeF3-Accelerated surface reconstruction of MoO2 nanosheets into coral-like CeF3/MoO2 composites enhances the oxygen evolution reaction for efficient water splitting.

Synergizing RuO2 with Fe-doped Co2RuO4 for boosting alkaline electrocatalytic oxygen evolution reaction.

Synergizing RuO2 with Fe-doped Co2RuO4 for boosting alkaline electrocatalytic oxygen evolution reaction.

Construction of crystalline/amorphous Ni2P/FePOx/graphene heterostructure by microwave irradiation for efficient oxygen evolution.

Construction of crystalline/amorphous Ni2P/FePOx/graphene heterostructure by microwave irradiation for efficient oxygen evolution.

Tailoring Polysulfide Interaction with Balanced d-Band Center via In Situ Construction of Atomically Dispersed Zr-Ox Sites in Mn2O3/β-MnO2 Heterostructure for Li-S Batteries.

Although noteworthy research focuses on heterostructured catalysts for efficient polysulfide adsorption in lithium-sulfur (Li-S) batteries, the strategy for maximized electrocatalytic activity is less investigated. Herein, Mn2O3/β-MnO2 heterostructure electrocatalyst is engineered via in situ regulation of atomically dispersed Zr4+ sites in the form of Zr-Ox coordinated-structure as a highly stable freestanding cathode. The fine-tuned Zr4+ sites can adjust polysulfide adsorption inducing reduced overpotential, improved Li+ mobility, and boosted redox kinetics. Their achievements are synergistically derived from the inhibition of polysulfide migration, utilization of 3D Li2S nucleation mechanism, and modification of the d-band center of electrocatalysts, resulting in crack-free anode-protection, diffusion-favorable Li2S deposition, and sustainable sulfur-reactions. Eventually, the Zr0.1-Mn2O3/β-MnO2@MWCNT cathode demonstrates a high initial capacity of 808mAhg-1 with a low average decay rate of 0.068% over 1000 cycles at 1C, even along with an impressive cyclic stability at 5C showing capacity up to 559.3mAhg-1 with a decay rate of only 0.170% over 200 cycles. Noteworthy, the electrocatalyst-applied cell achieves high areal capacity for half-/full-cell (N/P: 2.86) up to 4.45/3.88mAhcm-2 with 61.7/70.1% retention for 110/50 cycles under 4.6/5.4mgcm-2 sulfur loading with electrolyte in 8µLmgsulfur -1. This strategy highlights a new perspective to design an efficient cathode electrocatalyst for high-performance Li-S batteries.

Constructing Mn-Co-Fe Ternary Metal Phosphides Nanosheet Arrays as Bifunctional Electrocatalysts for Overall Water Splitting.

Bifunctional electrocatalysts with high efficiency, stability, and distinguished performance have attracted more and more attention in the field of overall water splitting, while the composition and structure design are very essential for electrocatalysts with superb performance and low price. In this work, the heterostructure Mn-Co-Fe-P nanoarrays is in situ grown on nickel foam (NF) by simple hydrothermal method and phosphating method. The resultant Mn-Co-Fe-P catalyst has favorable electrocatalytic performance with the oxygen evolution reaction (OER) overpotential at 10 (100) mA cm-2 of 192 (279) mV and the Tafel slope of 43.75mVdec-1, the hydrogen evolution reaction (HER) overpotential at 10 (100) mA cm-2 of 98 (152) mV and the Tafel slope of 40.68mVdec-1, and the full voltage of 1.66V at 100mAcm-2 when applied to overall water splitting. The 3D heterostructure provides more active sites, and the in situ growth improves the stability and conductivity of the catalyst. This binder-free heterostructure electrocatalyst with excellent stability and catalytic performance is a promising bifunctional electrocatalyst candidate for overall water splitting.

Highly Stable Bifunctional Heterostructured Electrocatalyst Integrated with LDPE-Derived Spherical Carbon for Longevous Alkaline Seawater Splitting.

The development of innovative electrocatalysts for seawater splitting shows great potential for large-scale green energy. Specifically, interface engineering plays a vital role in improving surface properties and charge transfer. However, seawater electrolysis encounters considerable challenges like chloride-induced corrosion, impurities, and microorganisms that hinder efficiency. Herein, we design a highly durable electrocatalyst based on selenium-enriched NiMn-Sx supported on low-density polyethylene-derived spherical carbon-Ni foam (Se-NiMnSx@SC/NF) using combination of pyrolysis and hydrothermal processes. The resulting Se-NiMnSx@SC/NF bifunctional catalyst with hollow cycas cone structure exhibited exceptional electrochemical performance and corrosion resistance in alkaline seawater with an ultralow overpotential of 146 and 262mV for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) to achieve a large current density of 500mA cm⁻2. In a simulated alkaline seawater splitting setup, the Se-NiMnSx@SC/NF catalyst maintained a cell voltage of 2.07V at 500mA cm⁻2, demonstrating outstanding durability for over 100 h with ≈100% Faradaic efficiency. Se and S doping in the heterostructured electrocatalyst refines the electronic structure and boosts reaction kinetics, while the hollow cycas cone design increases the exposure of active sites. Additionally, the carbon layer provided strong resistance to seawater corrosion, making Se-NiMnSx@SC/NF an excellent bifunctional catalyst for alkaline seawater electrolysis.

A Cellulose Pore Adsorption Strategy to Prepare CoFe/Co8FeS8 Heterostructures into N/S-Doped Carbon Cavities for Enhancing ORR/OER Performance.

To address the complex synthesis and metal agglomeration for partially sulfurized heterostructures, a cellulose pore adsorption strategy is proposed to fabricate CoFe/Co8FeS8 heterostructures in N/S-doped biocarbon cavities. In the absence of chelating agents, the porosity and active groups of cellulose enable the preadsorption of metal ions and N/S sources in willow catkin via ion adsorption and hydrogen bonding, respectively. The spatial confinement provided by biopores facilitates incomplete metal sulfuration while effectively preventing metal migration/aggregation. This catalyst demonstrates superior oxygen evolution and reduction reaction performance, with a minimal potential gap of 0.72 V in 0.1 mol·L-1 KOH, exceeding commercial Pt/C+RuO2. When applied in Zn-air batteries, the optimized electrode affords a high specific capacity of 803 mAh·gZn-1 and long-term cycling durability exceeding 500 h. These enhancements are attributed to the self-driven electron transfer between CoFe and Co8FeS8, and from the core to the carbon shell, which induces local electron enrichment at the interface, influencing the adsorption of key reactants. Besides, the ample N/S heteroatoms in the carbon shell further unlock extra active sites, and carbon cavities also inhibit metal nanoparticle shedding during testing, thereby enhancing electrocatalytic stability. This work offers a simple yet effective strategy for designing advanced heterostructure electrocatalysts.

Engineering N─TM(Co/Fe)─P Interfacial Electron Bridge in Transition Metal Phosphide/Nitride Heterostructure Nanoarray for Highly Active and Durable Hydrogen Evolution in Large‐Current Seawater Electrolysis

Abstract Hydrogen production via alkaline seawater electrolysis represents a promising strategy for future sustainable energy development. In this study, a FeCoP/TiN/CP(carbon paper) nanoarray electrode with exceptional hydrogen evolution reaction (HER) activity and durability at the industrial current density is successfully fabricated by engineering electronic coupling at the N─transition metal (TM, Co/Fe)─P interfacial bridge. Remarkably, the FeCoP/TiN/CP electrode requires only an overpotential of 129 mV (alkaline fresh water) and 152 mV (alkaline seawater) to achieve a current density of 500 mA cm−2, and stable operation is demonstrated for 2000 h in alkaline freshwater and 340 h in alkaline seawater at 500 mA cm−2 with negligible degradation. The superior HER performance stems from the unique nanoarray architecture and the phase interface N─TM(Co/Fe)─P bridge bonding, which enhances wettability, facilitates bubble release, and provides resistance to seawater corrosion. Theoretical calculations demonstrate that the interfacial N─TM(Co/Fe)─P bridging regulates the electronic structure of FeCoP, promoting water adsorption and dissociation, while optimizing the intermediate H* free energy. Furthermore, the covalent nature of the N‐TM(Co/Fe)‐P bridging, along with the strengthened Co/Fe‐P bonds, contributes to the superior stability of FeCoP/TiN/CP. This study not only provides new insights into the design of highly active heterostructure electrocatalysts, but also paves the new way for the practical and cost‐effective hydrogen production from seawater electrolysis.

*H Species Regulation of Heterostructured Cu2O/NiO Nanoflowers Boosting Tandem Nitrite Reduction for High‐Efficiency Ammonia Production

Abstract Ambient electrocatalytic reduction of NO2− to NH3 (NO2RR) provides a reliable route for migrating NO2− pollutants and simultaneously generating valuable NH3. However, the NO2RR involves multistep electron transfer and complex intermediates, rendering the achievement of high NH3 selectivity a major challenge. In this contribution, heterostructured Cu2O/NiO nanoflowers are explored for incorporating the advantages of dual active sites as a highly active and selective NO2RR catalyst. Combined theoretical calculations and in situ FTIR/EPR spectroscopy analysis, it is revealed the synergistic effect of Cu2O and NiO to promote the NO2RR energetics of Cu2O/NiO heterostructure electrocatalyst through a tandem catalysis pathway, where Cu2O activates the initial absorption and deoxygenation of NO2− for boosting *NO formation, while the generated *NO on Cu2O is then transferred on NiO substrate with abundant active hydrogen for NH3 conversion. Moreover, the heterostructure formation enhances *H retention capacity, promoting *H consumed in NO2RR and inhibiting inter‐*H species binding. As a result, Cu2O/NiO equipped in a flow cell displays a superior NH3 yield rate of 128.2 mg h−1 cm−2 and Faradaic efficiency of 97.1% at a high current density of −1.25 A cm−2. Further, this designed tandem system is proven to be adaptable for other electrochemical NH3 production reactions including NO3− reduction.