Mechanism Of Hydrogen Evolution Reaction Research Articles

Material Engineering Strategies for Efficient Hydrogen Evolution Reaction Catalysts.

Water electrolysis, a key enabler of hydrogen energy production, presents significant potential as a strategy for achieving net-zero emissions. However, the widespread deployment of water electrolysis is currently limited by the high-cost and scarce noble metal electrocatalysts in hydrogen evolution reaction (HER). Given this challenge, design and synthesis of cost-effective and high-performance alternative catalysts have become a research focus, which necessitates insightful understandings of HER fundamentals and material engineering strategies. Distinct from typical reviews that concentrate only on the summary of recent catalyst materials, this review article shifts focus to material engineering strategies for developing efficient HER catalysts. In-depth analysis of key material design approaches for HER catalysts, such as doping, vacancy defect creation, phase engineering, and metal-support engineering, are illustrated along with typical research cases. A special emphasis is placed on designing noble metal-free catalysts with a brief discussion on recent advancements in electrocatalytic water-splitting technology. The article also delves into important descriptors, reliable evaluation parameters and characterization techniques, aiming to link the fundamental mechanisms of HER with its catalytic performance. In conclusion, it explores future trends in HER catalysts by integrating theoretical, experimental and industrial perspectives, while acknowledging the challenges that remain.

The Bell-Evans-Polanyi relation for hydrogen evolution reaction from first-principles

The versatile Bell-Evans-Polanyi (BEP) relation stipulates the kinetics of a reaction in terms of thermodynamics. Herein, we establish the BEP relation for the hydrogen evolution reaction (HER) from fundamental electrochemical principles leveraging the Butler-Volmer relation for a one-step, one-electron process and the transition state theory. Based on first-principles investigations of HER mechanisms on fourteen metal electrodes, we firmly justify the BEP relation solely using an easy-to compute hydrogen adsorption free energy and universal electrochemical constants.

Allotrope-dependent activity-stability relationships of molybdenum sulfide hydrogen evolution electrocatalysts

Molybdenum disulfide (MoS2) is widely regarded as a competitive hydrogen evolution reaction (HER) catalyst to replace platinum in proton exchange membrane water electrolysers (PEMWEs). Despite the extensive knowledge of its HER activity, stability insights under HER operation are scarce. This is paramount to ensure long-term operation of Pt-free PEMWEs, and gain full understanding on the electrocatalytically-induced processes responsible for HER active site generation. The latter are highly dependent on the MoS2 allotropic phase, and still under debate. We rigorously assess these by simultaneously monitoring Mo and S dissolution products using a dedicated scanning flow cell coupled with downstream analytics (ICP-MS), besides an electrochemical mass spectrometry setup for volatile species analysis. We observe that MoS2 stability is allotrope-dependent: lamellar-like MoS2 is highly unstable under open circuit conditions, whereas cluster-like amorphous MoS3-x instability is induced by a severe S loss during the HER and undercoordinated Mo site generation. Guidelines to operate non-noble PEMWEs are therefore provided based on the stability number metrics, and an HER mechanism which accounts for Mo and S dissolution pathways is proposed.

Atomically Precise Mo2Cu17 Bimetallic Nanocluster: Synergistic Mo2O4-Coupled Copper Alkynyl Cluster for the Improved Hydrogen Evolution Reaction Performance.

Electrolytic hydrogen production via water splitting holds significant promise for the future of the energy revolution. The design of efficient and abundant catalysts, coupled with a comprehensive understanding of the hydrogen evolution reaction (HER) mechanism, is of paramount importance. In this study, we propose a strategy to craft an atomically precise cluster catalyst with superior HER performance by cocoupling a Mo2O4 structural unit and a Cu(I) alkynyl cluster into a structured framework. The resulting bimetallic cluster, Mo2Cu17, encapsulates a distinctive structure [Mo2O4Cu17(TC4A)4(PhC≡C)6], comprising a binuclear Mo2O4 subunit and a {Cu17(TC4A)2(PhC≡C)6} cluster, both shielded by thiacalix[4]arene (TC4A) and phenylacetylene (PhC≡CH). Expanding our exploration, we synthesized two homoleptic CuI alkynyl clusters coprotected by the TC4A and PhC≡C- ligands: Cu13 and Cu22. Remarkably, Mo2Cu17 demonstrates superior HER efficiency compared to its counterparts, achieving a current density of 10 mA cm-2 in alkaline solution with an overpotential as low as 120 mV, significantly outperforming Cu13 (178 mV) and Cu22 (214 mV) nanoclusters. DFT calculations illuminate the catalytic mechanism and indicate that the intrinsically higher activity of Mo2Cu17 may be attributed to the synergistic Mo2O4-Cu(I) coupling.

Recent Progress in High‐Entropy Alloy Electrocatalysts for Hydrogen Evolution Reaction

AbstractHigh‐entropy alloys (HEAs) materials, as promising nanomaterials, have garnered significant attention from researchers due to their excellent performance in the field of hydrogen evolution reaction (HER). The four core effects of HEAs, including the high‐entropy effect, severe lattice distortion effect, sluggish diffusion effect, and cocktail effect, are pivotal in underpinning their remarkable mechanical and thermodynamic properties. Nevertheless, the intricate geometric and electronic structures of HEAs make their catalytic mechanisms exceptionally complex and challenging to decipher. In particular, a thorough analysis of the underlying factors responsible for the outstanding catalytic activity, selectivity, and the ability to maintain stable hydrogen production, even at high current densities, in HEAs is lacking. To provide a systematic exploration of the design and application of HEAs in HER systems, this review commences with an examination of the physicochemical properties of HEAs. It covers a wide range of topics, including the synthesis methods of HEAs, and the major reaction mechanisms of HERs, and presents innovative methods and approaches for designing HEAs specifically in the context of HERs.

On the use of WO42− as a third component to Co–Mo ionic activator for HER in alkaline water electrolysis

This study investigates the impact of Co–Mo–W ionic activators on the hydrogen evolution reaction (HER) in alkaline electrolysis, comparing their performance to Co–Mo and Co–W systems. The research focuses on analyzing the catalytic efficiency of these activators under varying conditions, including temperature and current density variations. Key findings reveal that the Co–Mo–W activator enhances HER performance, with a significant 17% reduction in energy consumption compared to plain electrolyte, mirroring the efficiency of Co–Mo. Tafel analysis gave the insight of the reaction mechanism for HER for all activators, with Co–Mo–W exhibiting a lower Tafel slope, suggesting improved catalytic activity. Structural and morphological analysis of electrode coatings shows a highly developed surface for Co–Mo–W, with a roughness factor similar to or slightly lower than the most developed Co–Mo coating. The study concludes that the synergistic combination of Co, Mo, and W in a tri-component ionic activator offers a promising catalytic activity for HER, outperforming bi-component systems and presenting significant potential for industrial-scale alkaline water electrolysis applications.

Unraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in NiII Porphyrin Hydrides Using DFT Method.

Substituents at the meso-site of metalloporphyrins profoundly influence the hydrogen evolution reaction (HER) mechanism. This study employs density functional theory (DFT) to computationally analyze NiII-porphyrin and its hydrides derived from tetrakis(pentafluorophenyl)porphyrin molecules, presenting stereoisomers in ortho- or para-positions. The results reveal that the spatial resistance effect of meso-substituted groups at the ortho- and para-positions induces significant changes in Ni-N bond lengths, angles, and reaction dynamics. For ortho-position substituents forming complex I, a favorable 88.88 ų spherical space was created, facilitating proton coordination and the formation of H2 molecules; conversely, para-position substituents forming complex II impeded H2 formation until bimolecular complexes arose. Molecular dynamics (MD) analysis and comparison were conducted on the intermediation products of I-H2 and (II-H)2, focusing on the configuration and energy changes. In the I-H2 products, H2 molecules underwent separation after 150 fs and overcame the 2.2 eV energy barrier. Subsequently, significant alterations in the spatial structure were observed as complex I deformed. In the case of (II-H)2, it was influenced by the distinctive "sandwich" configuration; the spatial structure necessitated overcoming a 6.7 eV energy barrier for H2 detachment and a process observed after 2400 fs.

Fundamental Understanding of Hydrogen Evolution Reaction on Zinc Anode Surface: A First-Principles Study

HighlightsThe reaction mechanisms of hydrogen evolution reaction (HER) on various crystal surfaces of zinc anode have been systematically investigated by first-principle calculations.Both the thermodynamic and kinetic aspects of HER have been studied to reveal the relative HER activity of several crystal surface of zinc anode.The generalized coordination number of surface Zn atoms are proposed as a key descriptor of HER activity of Zn anode.

Design Strategies towards Advanced Hydrogen Evolution Reaction Electrocatalysts at Large Current Densities.

Hydrogen (H2 ), produced by water electrolysis with the electricity from renewable sources, is an ideal energy carrier for achieving a carbon-neutral and sustainable society. Hydrogen evolution reaction (HER) is the cathodic half-reaction of water electrolysis, which requires active and robust electrocatalysts to reduce the energy consumption for H2 generation. Despite numerous electrocatalysts have been reported by the academia for HER, most of them were only tested under relatively small current densities for a short period, which cannot meet the requirements for industrial water electrolysis. To bridge the gap between academia and industry, it is crucial to develop highly active HER electrocatalysts which can operate at large current densities for a long time. In this review, the mechanisms of HER in acidic and alkaline electrolytes are firstly introduced. Then, design strategies towards high-performance large-current-density HER electrocatalysts from five aspects including number of active sites, intrinsic activity of each site, charge transfer, mass transfer, and stability are discussed via featured examples. Finally, our own insights about the challenges and future opportunities in this emerging field are presented.

Stilbene-incorporated platinum(II) di-yne electrocatalysts for generating hydrogen from acetic acid

Molecular hydrogen (H2) is a potential alternative to fossil fuels since it is a green energy source with high energy density and non-polluting combustion materials. We present herein the electrochemical properties and hydrogen evolution reaction (HER) ability of two Pt(II) diynes (Pt-Sb-Pt & Sb-Pt-Sb) bearing stilbene unit. Both complexes catalyzed the HER in acidic media. In addition, density functional theory (DFT) calculation was carried out at B3LYP/LANL2DZ level of theory in gas phases as well as in the solvent (DMF) to delineate the possible mechanism of HER. We demonstrated that the studied Pt(II) electrocatalysts shift the reduction potential noticeably. However, no apparent role of photo-switchable stilbene fragment on electrolysis was observed and the presence of ethynyl moiety was necessary for stabilization of the metal center. To the best of our knowledge, this is the first study highlighting the electrocatalytic HER by platina-ynes.

A unique adsorption-diffusion-decomposition mechanism for hydrogen evolution reaction towards high-efficiency Cr, Fe-modified CoP nanorod catalyst

The rational construction of high-efficiency transition metal phosphides catalysts for hydrogen evolution reaction (HER) is crucial since their sluggish kinetics of water dissociation remain severe barriers for HER performance. The theoretical calculations indicate a unique adsorption-diffusion-decomposition mechanism for H2O molecules on CoP (111) surface. Herein, Fe could decrease H2O decomposition barrier energies and increase the amount of active sites, along with Cr could accelerate H2O adsorption, diffusion and increase the conductivity of the reaction surface. Aided by this mechanism, a self-supported electrode of Cr and Fe dual-doped CoP nanorod arrays grown on nickel foam was prepared. The electrode only requires an overpotential of 27 mV at 10 mA cm−2 for alkaline HER with excellent durability for 400 h. Moreover, the catalyst presents only 1.505 V at 10 mA cm−2 for alkaline water electrolysis. This work provides an in-depth understanding on catalytic mechanism of CoP-based materials.

Participation of electrochemically inserted protons in the hydrogen evolution reaction on tungsten oxides.

Understanding the mechanisms by which electrodes undergo the hydrogen evolution reaction (HER) is necessary to design better materials for aqueous energy storage and conversion. Here, we investigate the HER mechanism on tungsten oxide electrodes, which are stable in acidic electrolytes and can undergo proton-insertion coupled electron transfer concomitant with the HER. Electrochemical characterization showed that anhydrous and hydrated tungsten oxides undergo changes in HER activity coincident with changes in proton composition, with activity in the order HxWO3·H2O > HxWO3 > HxWO3·2H2O. We used operando X-ray diffraction and density functional theory to understand the structural and electronic changes in the materials at high states of proton insertion, when the oxides are most active towards the HER. H0.69WO3·H2O and H0.65WO3 have similar proton composition, structural symmetry, and electronic properties at the onset of the HER, yet exhibit different activity. We hypothesize that the electrochemically inserted protons can diffuse in hydrogen bronzes and participate in the HER. This would render the oxide volume, and not just the surface, as a proton and electron reservoir at high overpotentials. HER activity is highest in HxWO3·H2O, which optimizes both the degree of proton insertion and solid-state proton transport kinetics. Our results highlight the interplay between the HER and proton insertion-coupled electron transfer on transition metal oxides, many of which are non-blocking electrodes towards protons.

Nano-Scale Engineering of Heterojunction for Alkaline Water Electrolysis.

Alkaline water electrolysis is promising for low-cost and scalable hydrogen production. Renewable energy-driven alkaline water electrolysis requires highly effective electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). However, the most active electrocatalysts show orders of magnitude lower performance in alkaline electrolytes than that in acidic ones. To improve such catalysts, heterojunction engineering has been exploited as the most efficient strategy to overcome the activity limitations of the single component in the catalyst. In this review, the basic knowledge of alkaline water electrolysis and the catalytic mechanisms of heterojunctions are introduced. In the HER mechanisms, the ensemble effect emphasizes the multi-sites of different components to accelerate the various intermedium reactions, while the electronic effect refers to the d-band center theory associated with the adsorption and desorption energies of the intermediate products and catalyst. For the OER with multi-electron transfer, a scaling relation was established: the free energy difference between HOO* and HO* is 3.2 eV, which can be overcome by electrocatalysts with heterojunctions. The development of electrocatalysts with heterojunctions are summarized. Typically, Ni(OH)2/Pt, Ni/NiN3 and MoP/MoS2 are HER electrocatalysts, while Ir/Co(OH)2, NiFe(OH)x/FeS and Co9S8/Ni3S2 are OER ones. Last but not the least, the trend of future research is discussed, from an industry perspective, in terms of decreasing the number of noble metals, achieving more stable heterojunctions for longer service, adopting new craft technologies such as 3D printing and exploring revolutionary alternate alkaline water electrolysis.

Effect of Electrochemical Surface Oxidation on Intrinsic Activity Towards the Hydrogen Evolution Reaction of Ultra-Smooth Nanocrystalline Ni Thin Films

Green hydrogen has emerged as a leading contender in the pursuit of a sustainable energy transition, driving the need for optimized catalysts in hydrogen production. Therefore, considerable effort is taken to replace the highly active, yet expensive Pt-group metals with non-noble alternatives such as Ni. Understanding the hydrogen evolution reaction (HER) mechanism on well-performing Ni surfaces is essential for gaining fundamental knowledge and implementing this in practical applications. While high surface area structures are typically designed for enhanced efficiency, there is limited research available on the fundamental aspects of thin films and smooth surfaces, which are crucial for benchmarking intrinsic catalytic activity and elucidating catalytic mechanisms. To address this gap, we perform a combined microstructural and electrochemical evaluation of smooth Ni thin film electrodes to analyze HER in alkaline media.This study aimed to evaluate the intrinsic catalytic properties of nanocrystalline Ni thin films and the effect of electrochemical oxidation on the catalytic behavior, while precisely monitoring the evolution of the film surface state and roughness. In addition to experimental work, Density Functional Theory (DFT) calculations and Kinetic Monte Carlo (KMC) simulations are used to understand HER on oxide-modified Ni surfaces and the role of different elementary processes involved in the HER mechanism.Nanocrystalline low-roughness Ni electrodes for HER were produced via magnetron sputter deposition to minimize the difference between geometrical and electrochemical surface area. This means we find intrinsic material properties directly, bypassing the need for additional measurements for real surface area determination. The analysis of catalyst activities towards HER as well as the oxidation process [1] was performed via cyclic voltammetry, using a three-electrode setup. Within the conducted studies, we can report a significant lowering of the overpotential for HER upon in-situ oxidation of the electrodes due to the existence of NiO, and Ni(OH)2 on the Ni catalyst surface [2], leading also to a limitation of the deactivation processes. Further analysis including topography evaluation (AFM), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) in combination with selected area diffraction (SAED) of the as-deposited and oxidized electrodes confirmed that the observed effect can be assigned to the availability of oxides on the surface assuredly (Figure 1). Additionally, theoretical calculations and simulations (DFT, KMC) support the experimental data and derived theories.In conclusion, the beneficial effect of NiO and Ni(OH)2 presence on Ni surfaces was examined and successfully proven by a combination of electrochemical measurements, material characterization, theoretical calculations, and a careful experimental design that minimizes the influence of interfering factors, such as surface roughness.

(Digital Presentation) Electrochemical Hydrogen Production and Charge Storage Mechanisms on Mxenes Via in-Situ/Operando Raman Spectroelectrochemistry

The production of hydrogen fuel from water splitting through the hydrogen evolution reaction (HER) has been investigated for more than a century; yet, there exists no commercial water splitting device because of the lack of an efficient and cost-effective electrocatalyst. This scientific gap can be filled by the new class of two-dimensional carbides and nitrides, known as MXenes, if their mechanisms of electrocatalysis can be understood. Herein, we report on the electrocatalytic properties of MXenes and elucidate their mechanisms of electrocatalysis and charge storage. More specifically, we report on the detailed mechanisms of HER electrocatalysis and charge storage on the benchmark Ti3C2 carbide MXene in acidic (HCl) and neutral (Na2SO4) electrolytes using an in-situ/operando Raman spectroelectrochemical approach. This approach allows us to monitor, in real time, the structural behavior of the materials under operating conditions. The correlation between the Raman shifts and the current density provides insights into the mechanism of HER. In acidic electrolyte, we found that the HER mechanism proceeds through a surface protonation mechanism due to termination group changes, whereas neutral electrolyte HER undergoes an overcharging mechanism prior to splitting water to form hydrogen gas. For capacitive charge storage, we found that acidic electrolytes allow for pseudocapacitive behavior to take place in a similar surface protonation mechanism as for HER. In neutral electrolytes, the charge storage mechanism follows a purely double layer capacitance mechanism with sodium ions adsorbing and desorbing from the surface. The new knowledge from this work can be applied to a broad class of materials and systems to advance the field of energy conversion and storage.

Computational unravelling of cathodic hydride formation on palladium surfaces

Palladium (Pd) is well-known for its role in catalyzing hydrogen-based reduction reactions, owing to its excellent catalytic activity and hydrogen storage ability. Its surface and subsurface structures under electrochemical conditions are vital in understanding the hydrogen evolution reaction (HER) mechanism at the Pd cathodes where the most active sites are located on ‘in situ’ formed Pd-hydride layers. In this work, we investigate the process of Pd-hydride formation as well as the step-by-step formation and stability of Pd-hydride/Pd interfaces under electrochemical conditions using first-principles calculations. Our results reveal that among the low-indexed surfaces (111), (110) and (100), the (111) surface is expected to be the most dominant surface in a Pd nanostructure in addition to being the most preferred surface for hydrogen adsorption. Based on calculated Pourbaix diagrams, we can identify the relevant regions close to the equilibrium electrode potential and pH for proton electroreduction and hydrogen evolution, where the Pd surfaces start to be covered by hydrogen adatoms, and when the electrode potential is decreased, there are clear thermodynamic indications for more and more subsurface hydride layers. Overall, the results provide insights into the stability and formation of hydrogen-containing Pd surfaces, forming PdH/Pd type interfaces. Our idealized model systems are a first step towards elucidation of relevant active sites on Pd.

Recent Progress on Ruthenium-Based Electrocatalysts towards the Hydrogen Evolution Reaction

Hydrogen has emerged as an important candidate for clean energy, owing to its environmentally friendly advantages. Electrolytic hydrogen production stands out as the most promising technology for hydrogen production. Therefore, the design of highly efficient electrocatalysts is significant to drive the application of hydrogen technologies. Platinum (Pt)-based catalysts are famous for their outstanding performance in the hydrogen evolution reaction (HER). However, the expensive cost limits its wide application. Ruthenium (Ru)-based catalysts have received extensive attention due to their relatively lower cost and HER performance similar to that of Pt. Nevertheless, the performance of Ru-based catalysts is still unable to meet industrial demands. Therefore, improving HER performance through the modification of Ru-based catalysts remains significant. In this review, the reaction mechanism of HER is analyzed and the latest research progress in the modification of Ru-based electrocatalysts is summarized. From the reaction mechanism perspective, addressing the adsorption of intermediates on the Ru-based electrocatalyst surface, the adsorption–activation of interface water molecules, and the behavior of interface water molecules and proposing solutions to enhance performance of Ru-based electrocatalyst are the main findings, ultimately contributing to promoting their application in the field of electrocatalysis.

Nitrogen-doped 3D micro-coral Cd(O,S) for highly efficient zero-VRHE solar-to-hydrogen photocathode

Solar-light-driven hydrogen (H2) production is considered one of the most promising methods for clean energy generation to replace fossil fuel-based energy. Herein, we report a highly efficient 3D coral-like N-doped cadmium oxysulfide (Cd(O,S)) photocathode for hydrogen evolution reaction (HER) in an alkaline solution. The N5Cd(O,S) with a certain nitrogen amount achieved an onset potential of 0.63 VRHE with a photocurrent density of 0.74 mAˑcm−2 at 0 VRHE and solar-to-hydrogen efficiency (ηSTH) of 6.6 %. In a practical application, the amount of evolved H2 by N5Cd(O,S) photocathode was 12.3 μmol·cm−2 performed at 0 VRHE, improved 2-folds from Cd(O,S) without N dopant. Moreover, N5Cd(O,S) exhibited excellent stability of 95.8 % for over 10 h HER testing. This work reveals that N5Cd(O,S) photocathode can capture incident light efficiently within the 3D coral-like microstructure and the contained oxygen vacancies (OVs) in N5Cd(O,S) play a dominant role for photoelectrochemical H2 generation. A specific HER mechanism is proposed based on the experimental results to elucidate the improved photoelectrocatalytic activity.

Toward effective electrocatalytic C–N coupling for the synthesis of organic nitrogenous compounds using CO2 and biomass as carbon sources

AbstractThermochemical conversion of fossil resources into fuels, chemicals, and materials has rapidly increased atmospheric CO2 levels, hindering global efforts toward achieving carbon neutrality. With the increasing push for sustainability, utilizing electrochemical technology to transform CO2 or biomass into value‐added chemicals and to close the carbon cycle with sustainable energy sources represents a promising strategy. Expanding the scope of electrosynthesis technology is a prerequisite for the electrification of chemical manufacturing. To this end, constructing the C─N bond is considered a priority. However, a systematic review of electrocatalytic processes toward building C─N bonds using CO2 and biomass as carbon sources is not available. Accordingly, this review highlights the research progress in the electrosynthesis of organic nitrogen compounds from CO2 and biomass by C─N coupling reactions in view of catalytic materials, focusing on the enlightenment of traditional catalysis on C─N coupling and the understanding of the basis of electrochemical C─N coupling. The possibility of C─N bond in electrocatalysis is also examined from the standpoints of activation of substrates, coupling site, mechanism, and inhibition of hydrogen evolution reaction (HER). Finally, the challenges and prospects of electrocatalytic C─N coupling reactions with improved efficiency and selectivity for future development are discussed.

Optimizing Pt-Based Alloy Electrocatalysts for Improved Hydrogen Evolution Performance in Alkaline Electrolytes: A Comprehensive Review.

The splitting of water through electrocatalysis offers a sustainable method for the production of hydrogen. In alkaline electrolytes, the lack of protons forces water dissociation to occur before the hydrogen evolution reaction (HER). While pure Pt is the gold standard electrocatalyst in acidic electrolytes, since the 5d orbital in Pt is nearly fully occupied, when it overlaps with the molecular orbital of water, it generates a Pauli repulsion. As a result, the formation of a Pt-H* bond in an alkaline environment is difficult, which slows the HER and negates the benefits of using a pure Pt catalyst. To overcome this limitation, Pt can be alloyed with transition metals, such as Fe, Co, and Ni. This approach has the potential not only to enhance the performance but also to increase the Pt dispersion and decrease its usage, thus overall improving the catalyst's cost-effectiveness. The excellent water adsorption and dissociation ability of transition metals contributes to the generation of a proton-rich local environment near the Pt-based alloy that promotes HER. Significant progress has been achieved in comprehending the alkaline HER mechanism through the manipulation of the structure and composition of electrocatalysts based on the Pt alloy. The objective of this review is to analyze and condense the latest developments in the production of Pt-based alloy electrocatalysts for alkaline HER. It focuses on the modified performance of Pt-based alloys and clarifies the design principles and catalytic mechanism of the catalysts from both an experimental and theoretical perspective. This review also highlights some of the difficulties encountered during the HER and the opportunities for increasing the HER performance. Finally, guidance for the development of more efficient Pt-based alloy electrocatalysts is provided.