Alkaline Hydrogen Oxidation Reaction Research Articles

Atomically dispersed Iridium on Mo2C as an efficient and stable alkaline hydrogen oxidation reaction catalyst

Hydroxide exchange membrane fuel cells (HEMFCs) have the advantages of using cost-effective materials, but hindered by the sluggish anodic hydrogen oxidation reaction (HOR) kinetics. Here, we report an atomically dispersed Ir on Mo2C nanoparticles supported on carbon (IrSA-Mo2C/C) as highly active and stable HOR catalysts. The specific exchange current density of IrSA-Mo2C/C is 4.1 mA cm−2ECSA, which is 10 times that of Ir/C. Negligible decay is observed after 30,000-cycle accelerated stability test. Theoretical calculations suggest the high HOR activity is attributed to the unique Mo2C substrate, which makes the Ir sites with optimized H binding and also provides enhanced OH binding sites. By using a low loading (0.05 mgIr cm−2) of IrSA-Mo2C/C as anode, the fabricated HEMFC can deliver a high peak power density of 1.64 W cm−2. This work illustrates that atomically dispersed precious metal on carbides may be a promising strategy for high performance HEMFCs.

Balancing the Binding of Intermediates Enhances Alkaline Hydrogen Oxidation on D-Band Center Modulated Pd Sites.

Exploring efficient alkaline hydrogen oxidation reaction (HOR) electrocatalysts is of great concern for constructing anion exchange membrane fuel cells (AEMFCs). Herein, d-band center modulated PdCo alloys with ultralow Pd content anchored onto the defective carbon support (abbreviated as PdCo/NC hereafter) are proposed as highly efficient HOR catalyst. The as-prepared catalyst exhibits exceptional HOR performance compared to the Pt/C catalyst, achieving thermodynamically spontaneous and kinetically preferential reactions. Specifically, the resultant PdCo/NC demonstrates a marked enhancement in alkaline HOR performance, with the highest mass and specific activities of 1919.6 mA mgPd-1 and 1.9 mA cm-2, 51.1 and 4.2 times higher than those of benchmark of Pt/C, along with an excellent stability in a chronoamperometry test. In the analysis of in situ Raman spectra, it was discovered that tetrahedrally coordinated H-bonded water molecules were formed during the HOR process. This indicates that the promotion of interfacial water molecule formation and enhancement of HOR activities in PdCo/NC are facilitated by defect engineering and the turning of d-band center in PdCo alloy. The essential knowledge obtained in this study could open up a new direction for modifying the electronic structure of cost-effective HOR catalysts through electronic structure engineering.

Unraveling Stoichiometry Effect in Nickel‐Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes

Anion‐exchange membrane fuel cells provide the possibility to use platinum group metal‐free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel‐tungsten (Ni‐W) alloy catalysts, we show that the Ni:W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen‐bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state‐of‐the‐art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next‐generation catalysts for fuel cells.

Unraveling Stoichiometry Effect in Nickel-Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes.

Anion-exchange membrane fuel cells provide the possibility to use platinum group metal-free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel-tungsten (Ni-W) alloy catalysts, we show that the Ni:W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen-bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state-of-the-art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next-generation catalysts for fuel cells.

Two-dimensional flake Co/Co2N0.67 modified by molybdenum oxides achieves enhancement of bifunctional hydrogen electrocatalysis

To address the urgent need for non-precious metal-based catalysts in the industrial preparation and application of hydrogen energy, we present a secondary hydrothermal strategy to prepare a Mo-modified cobalt carbonate precursor, resulting in the Mo–Co/Co2N0.67 catalyst. The cobalt-based materials exhibit a layered flake structure due to molybdenum modification, exposing more active sites, while molybdenum oxide modification enhances hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). In alkaline HER measurements, Mo–Co/Co2N0.67 achieves a remarkable current density of 10 mA cm−2 at only 27 mV. The overall water splitting of Mo–Co/Co2N0.67 + RuO2 can reach 10 mA cm−2 at 1.52 V voltage. In alkaline HOR measurements, it exhibits the current density of 2.92 mA cm−2@0.1 V vs. RHE and an exchange current density (J0) of 2.96 mA cm−2. This work highlights the effective regulation of non-noble metal-based electrocatalysts through Mo modification, providing valuable insights for the development of efficient non-precious metal-based hydrogen electrocatalysis within the context of anion exchange membrane unitized reversible fuel cells (AEM-URFC).

One‐Pot Synthesis of Carbon‐Supported Pd Nanoparticles with Ni and Carbon Matrix Protection for Durable Alkaline Hydrogen Oxidation Reaction

Protecting nanoparticles with a carbon matrix can enhance the durability of the catalysts in alkaline fuel cells (AFC) and is well‐documented. While others have tried complex syntheses to produce small nanoparticle catalysts, in this work, in order to scale‐up batches of 15 g or more, carbon‐cap (or carbon‐coating) protected Vulcan XC72‐supported Pd‐Ni (1‐2) nanoparticles (Pd‐Niacc/C) were successfully synthesized via a one‐step dry‐synthesis process. This catalyst was compared with a commercial Pd‐Ni/Vulcan XC72 material (PdNi/C, Premetek) in terms of hydrogen oxidation reaction (HOR) activity and stability. To produce less ordered carbon caps (versus graphite/graphene), a low‐temperature heat‐treatment (below 500°C) was used, resulting in Pd‐Niacc/C of unique electrochemical properties: easily electrochemically activated, this catalyst outperforms PdNi/C for alkaline HOR and proves more durable under highly oxidizing accelerated stress test (AST) conditions. Identical location transmission electron microscopy (ILTEM), X‐ray photoelectron spectroscopy (XPS) and rotating disk electrode (RDE) measurements demonstrate how the Ni‐rich surface plays an important role in HOR activity for both PdNi/C and PdNiacc/C and that the protective carbon‐coating of the latter ensures better durability of performance and better resistance to materials degradation.

Temperature-Induced Interface Hybridization of WC Boosts NiCu Activity for Alkaline Hydrogen Oxidation Reaction.

The development of non-precious hydrogen oxidation reaction (HOR) catalysts is a major challenge for the commercialization of Pt-free fuel cells. Herein, a temperature-induced phase hybridization method is reported that greatly improves the catalytic performance of NiCu alloy for the HOR. The migration of W atoms hybridizes the interface of tungsten oxide (WOx) and tungsten carbide (WC) at the onset reduction temperature of WOx, leading to a greatly weakened H binding energy and an optimized OH binding energy, which endows NiCuW/WOx-WC@WC with favorable stability and CO resistance during HOR. The hybridization catalysts deliver a high mass activity of 29.37 mA mg-1 Ni and reach a peak power of 298 mW.cm-2 in H2-O2 anion exchange membrane fuel cells (AEMFCs).

Synergistic interactions of electronic modulation and low crystallization in Ru-RuO2/C heterostructure for highly efficient multifunctional electrocatalysis

Developing electrocatalysts with multifunctional performance is crucial for hydrogen energy storage and conversion, but still a great challenge. Herein, an efficient trifunctional electrocatalyst with heterostructure is fabricated by a sequential reduction and annealing approach. With different annealing atmospheres, Ru-RuO2/C electrocatalysts having different Ru/RuO2 atomic ratios or different crystallinities were achieved. Among these electrocatalysts, Ru-RuO2/C annealed from N2-air mixed atmosphere (Ru-RuO2/C 250NA) displays the most excellent performance, affording overpotential values of 30.63 mV for alkaline hydrogen evolution reaction (HER) and 273.42 mV for alkaline oxygen evolution reaction (OER) at 10 mA cm−2, much lower than those of state-of-the-art Pt/C (η10, HER = 46.57 mV) and RuO2 (η10, OER = 288.99 mV). Not only that, it also delivers favorable activity for alkaline hydrogen oxidation reaction (HOR), with 2.1 times of mass specific exchange current density than that of Pt/C. The experimental and theoretical investigations prove the electron rearrangement at Ru and RuO2 interface with abundant defects and amorphous/crystalline structures. The synergistic effect of dual active sites simultaneously optimizes H and OH as well as H2O adsorption energies, endowing the Ru-RuO2/C 250NA as the preferential electrocatalysts.

Charge distribution modulation of hollow flower-like tungsten doped nickel nitride for alkaline hydrogen oxidation

Exploring efficient nickel (Ni)-based catalysts for alkaline hydrogen oxidation reaction (HOR) to replace platinum group metal (PGM) is highly essential for the development of anion exchange membrane fuel cells. Nevertheless, the HOR activity of Ni is far away from PGM owing to the strong hydrogen adsorption. Herein, the tungsten-doped nickel nitride (W-Ni3N) with modulated local charge distribution and hollow flower structure is presented to improve the HOR performance. Mechanism studies reveal that W doping induces the redistribution of local charge around Ni sites due to the electron transfer from Ni to W, which strengthens the hydroxyl adsorption and simultaneously weakens hydrogen adsorption. Benefitting from the optimized adsorption of HOR intermediates and hollow flower structure, W-Ni3N exhibits improved intrinsic activity and mass activity, which are 1.7 and 10 times higher than that of pure Ni3N, respectively. This work presents a promising way to design cost-effective electrocatalysts by fine-tuning the electronic structure.

Stable and High-performance Flow H2 -O2 Fuel Cells with Coupled Acidic Oxygen Reduction and Alkaline Hydrogen Oxidation Reactions.

Conventional H2 -O2 fuel cells suffer from the low output voltage, insufficient durability, and high-cost catalysts (e.g., noble metals). Herein, this work reports a conceptually new coupled flow fuel cell (CF-FC) by coupling asymmetric electrolytes for acidic oxygen reduction reaction and alkaline hydrogen oxidation reaction. By introducing an electrochemical neutralization energy, the newly-developed CF-FCs possess a significantly increased theoretical open-circuit voltage. Specifically, a CF-FC based on a typical transition metal single-atom Fe-N-C cathode catalyst demonstrates a high electricity output up to 1.81V and durability with an ultrahigh retention of 91% over 110h, far superior to the conventional fuel cells (usually, < 1.0V, < 50% retention over 20h). The output performance can even be significantly enhanced easily by connecting multiple CF-FCs into the parallel, series, or combined parallel-series connections at a fractional cost of that for the conventional H2 -O2 fuel cells, showing great potential for large-scale practical applications. Thus, this study provides a platform to transform conventional fuel cell technology through the rational design and development of advanced energy conversion and storage devices by coupling different electrocatalytic reactions.

Activating and Identifying the Active Site of RuS2 for Alkaline Hydrogen Oxidation Electrocatalysis.

Searching for highly efficient and economical electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is crucial for the development of alkaline polymer membrane fuel cells. Here, we report a valid strategy to active pyrite-type RuS2 for alkaline HOR electrocatalysis by introducing sulfur vacancies. The obtained S-vacancies modified RuS2-x exhibits outperformed HOR activity with a current density of 0.676 mA cm-2 and mass activity of 1.43 mA μg-1, which are 15-fold and 40-fold improvement than those of Ru catalyst. In situ Raman spectra demonstrate the formation of S-H bond during the HOR process, identifying the S atom of RuS2-x is the real active site for HOR catalysis. Density functional theory calculations and experimental results including in situ surface-enhanced infrared absorption spectroscopy suggest the introduction of S vacancies can rationally modify the p orbital of S atoms, leading to enhanced binding strength between the S sites and H atoms on the surface of RuS2-x, together with the promoted connectivity of hydrogen-bonding network and lowered water formation energy, contributes to the enhanced HOR performance.

Activating and Identifying the Active Site of RuS2 for Alkaline Hydrogen Oxidation Electrocatalysis

AbstractSearching for highly efficient and economical electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is crucial for the development of alkaline polymer membrane fuel cells. Here, we report a valid strategy to active pyrite‐type RuS2 for alkaline HOR electrocatalysis by introducing sulfur vacancies. The obtained S‐vacancies modified RuS2−x exhibits outperformed HOR activity with a current density of 0.676 mA cm−2 and mass activity of 1.43 mA μg−1, which are 15‐fold and 40‐fold improvement than those of Ru catalyst. In situ Raman spectra demonstrate the formation of S−H bond during the HOR process, identifying the S atom of RuS2−x is the real active site for HOR catalysis. Density functional theory calculations and experimental results including in situ surface‐enhanced infrared absorption spectroscopy suggest the introduction of S vacancies can rationally modify the p orbital of S atoms, leading to enhanced binding strength between the S sites and H atoms on the surface of RuS2−x, together with the promoted connectivity of hydrogen‐bonding network and lowered water formation energy, contributes to the enhanced HOR performance.

Unveiling the nature of Pt-induced anti-deactivation of Ru for alkaline hydrogen oxidation reaction

While Ru owns superior catalytic activity toward hydrogen oxidation reaction and cost advantages, the catalyst deactivation under high anodic potential range severely limits its potential to replace the Pt benchmark catalyst. Unveiling the deactivation mechanism of Ru and correspondingly developing protection strategies remain a great challenge. Herein, we develop atomic Pt-functioned Ru nanoparticles with excellent anti-deactivation feature and meanwhile employ advanced operando characterization tools to probe the underlying roles of Pt in the anti-deactivation. Our studies reveal the introduced Pt single atoms effectively prevent Ru from oxidative passivation and consequently preserve the interfacial water network for the critical H* oxidative release during catalysis. Clearly understanding the deactivation nature of Ru and Pt-induced anti-deactivation under atomic levels could provide valuable insights for rationally designing stable Ru-based catalysts for hydrogen oxidation reaction and beyond.

Tuning the apparent hydrogen binding energy to achieve high-performance Ni-based hydrogen oxidation reaction catalyst

High-performance platinum-group-metal-free alkaline hydrogen oxidation reaction catalysts are essential for the hydroxide exchange membrane fuel cells, which generally require high Pt loadings on the anode. Herein, we report a highly active hydrogen oxidation reaction catalyst, NiCuCr, indicated by the hydroxide exchange membrane fuel cell with a high peak power density of 577 mW cm−2 (18 times as high as the Ni/C anode) and a stability of more than 150 h (a degradation rate slower by 7 times than the Ni/C anode). The spectroscopies demonstrate that the alloy effect from Cu weakens the hydrogen binding, and the surface Cr2O3 species enhance the interfacial water binding. Both effects bring an optimized apparent hydrogen binding energy and thus lead to the high hydrogen oxidation reaction performance of NiCuCr. These results suggest that the apparent hydrogen binding energy determines the hydrogen oxidation reaction performance and that its tuning is beneficial toward high electrocatalytic performance.

Implanting oxophilic metal in PtRu nanowires for hydrogen oxidation catalysis

Bimetallic PtRu are promising electrocatalysts for hydrogen oxidation reaction in anion exchange membrane fuel cell, where the activity and stability are still unsatisfying. Here, PtRu nanowires were implanted with a series of oxophilic metal atoms (named as i-M-PR), significantly enhancing alkaline hydrogen oxidation reaction (HOR) activity and stability. With the dual doping of In and Zn atoms, the i-ZnIn-PR/C shows mass activity of 10.2 A mgPt+Ru−1 at 50 mV, largely surpassing that of commercial Pt/C (0.27 A mgPt−1) and PtRu/C (1.24 A mgPt+Ru−1). More importantly, the peak power density and specific power density are as high as 1.84 W cm−2 and 18.4 W mgPt+Ru−1 with a low loading (0.1 mg cm−2) anion exchange membrane fuel cell. Advanced experimental characterizations and theoretical calculations collectively suggest that dual doping with In and Zn atoms optimizes the binding strengths of intermediates and promotes CO oxidation, enhancing the HOR performances. This work deepens the understanding of developing novel alloy catalysts, which will attract immediate interest in materials, chemistry, energy and beyond.

Optimizing Nickel Orbital Occupancy via Co‐Modulation of Core and Shell Structures to Accelerate Alkaline Hydrogen Electro‐Oxidation Reaction

AbstractNickel‐based catalysts are recognized as a promising alternative to platinum‐based catalysts for the alkaline hydrogen oxidation reaction (HOR) yet suffer from poor stability and relatively low activity. Herein, a nitrogen ligand‐assisted approach is reported to encapsulate nickel‐copper nanoparticles within few carbon layers, and by modulating the core and shell components/structure, the charge distribution in the nanostructures can be finely regulated. The optimized Ni93Cu7@NC catalyst exhibits outstanding HOR activity with an intrinsic activity of 61.0 µA cm−2 and excellent stability, which is among the most advanced Ni‐based HOR catalysts. Notably, an alkaline exchange membrane fuel cell utilizing this catalyst achieves a peak power density of 381 mW cm−2 and maintains stability at 100 mA cm−2 for over 24 h. Experimental and theoretical investigations unveil that the electron re‐distribution at the interface of NiCu core and nitrogen‐doped carbon reduces the electron occupancy in Ni 4s‐H 1s bonding orbitals and Ni 3dz2/yz‐O 2p antibonding orbitals, leading to a weakened hydrogen binding energy and enhance hydroxide binding energy. Consequently, the limiting energy for the HOR is reduced following a bifunctional mechanism on the Ni93Cu7@NC. This work provides a core‐shell co‐modulation strategy to accurately regulate the electronic structure of transition metals to design robust catalysts.

Construction of Heterostructure between Ni17W3 and WO2 to Boost the Hydrogen Oxidation Reaction in Alkaline Medium.

The inferior intrinsic performance of Ni-based catalysts for the hydrogen oxidation reaction (HOR) in an alkaline medium seriously restricts the utilization of emerging anion-exchange membrane fuel cells (AEMFCs). This is because the hydrogen and hydroxyl binding energies on Ni need to be optimized. Although electrocatalysts obtained by alloying Ni with Mo or W reportedly exhibit enhanced activity, they are still far from industrial requirements based on unbalanced HBE and OHBE. Herein, we report to further enhance alkaline HOR activity by constructing a heterostructure between NiW alloy and metal oxide (Ni17W3/WO2), which is synthesized through solvothermal treatment combined with annealing. The as-fabricated reduced graphene oxide (rGO)-supported Ni17W3/WO2 (Ni17W3/WO2/rGO) exhibits state-of-the-art catalytic activity (current density of 2.9 mA cm-2 at 0.1 V vs RHE), faster kinetics (geometric kinetics current density of 4.0 mA cm-2 that can be comparable to Pt/C), and high stability (maintaining the current density for more than 80 h) toward HOR in alkaline media. The detailed characterizations reveal that the charge transfer across the boundary arising from constructing the as-prepared heterostructure tunes the electronic structures, ultimately facilitating the HOR process.

Revealing the role of a bridging oxygen in a carbon shell coated Ni interface for enhanced alkaline hydrogen oxidation reaction.

Encapsulating metal nanoparticles inside carbon layers is a promising approach to simultaneously improving the activity and stability of electrocatalysts. The role of carbon layer shells, however, is not fully understood. Herein, we report a study of boron doped carbon layers coated on nickel nanoparticles (Ni@BC), which were used as a model catalyst to understand the role of a bridging oxygen in a carbon shell coated Ni interface for the improvement of the hydrogen oxidation reaction (HOR) activity using an alkaline electrolyte. Combining experimental results and density functional theory (DFT) calculations, we find that the electronic structure of Ni can be precisely tailored by Ni-O-C and Ni-O-B coordinated environments, leading to a volcano type correlation between the binding ability of the OH* adsorbate and HOR activity. The obtained Ni@BC with a optimized d-band center displays a remarkable HOR performance with a mass activity of 34.91 mA mgNi-1, as well as superior stability and CO tolerance. The findings reported in this work not only highlight the role of the OH* binding strength in alkaline HOR but also provide guidelines for the rational design of advanced carbon layers used to coat metal electrocatalysts.

Recent advances in metal-based electrocatalysts: from fundamentals and structural regulations to applications in anion-exchange membrane fuel cells

We present a comprehensive understanding of the alkaline hydrogen oxidation reaction (HOR), ammonium oxidation reaction (AOR), and oxygen reduction reaction (ORR) based on metal catalysts for H2 or NH3-fueled alkaline exchange membrane fuel cells.

Hydrogen oxidation electrocatalysts for anion-exchange membrane fuel cells: activity descriptors, stability regulation, and perspectives

The general principles in terms of reactivity and stability to design efficient electrocatalysts for the alkaline hydrogen oxidation reaction are reviewed. The performance of catalysts in anion-exchange membrane fuel cells is further discussed.