Low loading of P modified Rh nanoparticles encapsulated in N,P-doped carbon for boosted and pH-universal hydrogen evolution reaction

Searching for highly efficient and Pt-free electrocatalysts with comparable hydrogen evolution reaction (HER) activities to the benchmark Pt/C catalyst is highly demanded for developing renewable water electrolysis system but still remains challenging. In the current work, low loading of P modified ultrafine Rh nanoparticles encapsulated in N, P dual-doped carbon layers (Rh–P@NPC) have been prepared through a facile polymerization-impregnation followed by high-temperature pyrolysis process. Benefiting from the unique core-shell structural advantages and synergistic effect of Rh–P and NPC components, the resulting Rh–P@NPC catalyst not only exhibits remarkable electrocatalytic activity for HER in the whole pH range with a low overpotential of 31 mV, 65 mV, and 130 mV to drive a current density of 10 mA cm^?2 in 0.5 M H₂SO₄, 1.0 M KOH, and 1.0 M PBS, respectively, but also demonstrates high durability. It is worth to note that all these HER performances are on a par with commercial Pt/C catalysts for HER. This synthetic strategy provides possibility for the fabrication of carbon-based heterostructures with high catalytic activity and durability in harsh environments.     

Metal-rich heterostructure of Ag-doped FeS/Fe2P for robust hydrogen evolution

The transition metal phosphides (TMPs) with highly active and low-cost are imperative electrocatalysts for hydrogen evolution reaction (HER). In particular, metal-rich interface engineering of iron phosphide could effectively modify the active sites for HER and accelerate the charge transfer, thus achieving the promoted efficiency. Herein, we report metal-rich heterostructure of Ag-doped Fe₂P shell attached to FeS core on Fe foams (FeS/Fe₂P–Ag@IF) for HER, which are synthesized by a simple hydrothermal method with subsequent low-temperature phosphorization. Notably, the phosphorization process simultaneously achieves the partial conversion of FeS to Fe₂P, and complete reduction of Ag₂S to Ag. Furthermore, the metal-rich structure of Fe₂P increases the active sites for hydrogen adsorption, which consequently contributes to hydrogen evolution. Simultaneously, the successful doping of metallic Ag enhanced the electroconductivity and the stability of the electrocatalyst. Benefiting from the ternary synergistic effect at FeS/Fe₂P–Ag@IF and metallic Ag doping, the optimal Ag-doped FeS/Fe₂P electrocatalyst exhibits a low overpotential of 214.9 mV at 100 mA cm^?2, even surviving at this large current density with long-term stability. This promising strategy involving metallic Ag doping may be a suitable option for the development of iron-based metal-rich phosphides heterostructured for HER.     

Facile synthesis of Ni5P4 nanosheets/nanoparticles for highly active and durable hydrogen evolution

It is essential to search highly active, steady and cheap non-noble electrocatalyst for hydrogen evolution reaction (HER). At present, nickel phosphides are extensively used in electrochemical hydrogen evolution due to its excellent stability and activity. Hence, we report a facile, effective and feasible strategy to synthesis of Ni₅P₄ nanosheets/nanoparticles structure on carbon cloth, which was fabricated by electroless nickel plating on carbon cloth followed via straightforward thermal phosphidation treatment with NaH₂PO₂ as phosphorus source. The as-prepared CC@Ni–P electrocatalyst exhibits HER activity with low overpotentials (93 mV vs. RHE) to attain current density 10 mA/cm² as well as small Tafel slope (58.2 mV/dec), which outperforms most nickel phosphides electrocatalysts. The excellent HER performance can be ascribed to the large electrochemically active surface area, and phosphorus-rich Ni₅P₄ phase can supply further bridges sites of Ni and P. Significantly, as-prepared CC@Ni–P catalyst electrode exhibits no apparent HER activity decay after continuous stability test. Beyond that, the approach can be readily used to fabricate large size (5 × 5 cm) nickel phosphide electrocatalyst with excellent HER performance, which may be conducive to the proton exchange membrane (PEM) water electrolyser applications in future. This work opens an effective way to construct excellent performance transition-metal phosphides for HER.     

Embedding Co2P nanoparticles into co-doped carbon hollow polyhedron as a bifunctional electrocatalyst for efficient overall water splitting

The reasonable design and construction of non-precious metal electrocatalysts with low cost and high performance is critical for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a facile polymerization-pyrolysis method is proposed to encapsulate Co₂P nanoparticles in co-doped hollow carbon shell by using ZIF-67 and P-containing polymers as precursor. The unique construction not only effectively prevents nanoparticles from detaching, showing good stability after long-term testing, but also provides abundant active sites, large surface areas and large pore volumes, enabling the electrolyte and electrode material to full contact. As expected, the Co₂P/NPSC-800 performs superior HER performance with low overpotential of 173 mV at 10 mA cm⁻² and excellent stability of 88% retention for 35 h and OER performance with low overpotential of 320 mV at 10 mA cm⁻², which endows Co₂P/NPSC-800 with good catalytic activity in overall water splitting. Furthermore, density functional theory (DFT) calculations reveal that the metallic property and the decreased reaction barriers of Co₂P can promote the catalytic reactions. This work offers an effective route in synthesizing other transition metal phosphides with high catalytic properties.     

Facile preparation of large-area self-supported porous nickel phosphide nanosheets for efficient electrocatalytic hydrogen evolution

Metal phosphide structures have been widely explored for electrocatalytic hydrogen evolution reaction (HER) owing to their high activity and durability, and the phosphidation reaction is very important for the preparation of metal phosphides. In this paper, we reported a facile, effective, and practical phosphidation strategy to prepare nickel phosphide structures by placing a Ni foam above the red phosphorus powder with a distance of 1 cm in a covered crucible. As-prepared self-supported hierarchical Ni₅P₄/NiP₂ biphase porous nanosheets exhibited an excellent HER activity. The overpotential for a current density of 10 mA/cm² and the Tafel slope are as low as 92 mV and 52.8 mV/dec, respectively, both of which are much better than those delivered by the Ni₅P₄ nanosheets prepared by the conventional carry-gas upstream-downstream method. The complete phosphidation reaction, high electrochemically active surface area, and the Ni₅P₄/NiP₂ biphasic synergistic effect account for the outstanding HER performance. Moreover, the porous Ni₅P₄/NiP₂ nanosheets exhibited excellent stability under both accelerated degradation test and long-term durability test. Besides, this method can be employed to prepare large-area self-supported hierarchical porous Ni₅P₄/NiP₂ nanosheets with nearly same HER activities and long-term stability, suggesting a high potential for practical application.     

PBA derived FeCoP nanoparticles decorated on NCNFs as efficient electrocatalyst for water splitting

Transition metal phosphides have been known as promising electrocatalysts for hydrogen evolution and oxygen evolution reactions (HER and OER) due to their high catalytic activity. In this work, the FeCoP nanoparticles decorated on N-doped electrospun carbon nanofibers (FeCoP@NCNFs) was successfully synthesized through depositing Fe, Co-based Prussian blue analogue Co₃[Fe(CN)₆]₂·10H₂O (FeCo-PBA) onto the electrospun PVP/PAN nanofibers via layer-by-layer approach, followed by carbonization and phosphorization treatments. Benefiting from the high electrical conductivity, abundant catalytic active sites and the synergistic effect between FeCoP nanoparticles and N-doped carbon nanofibers network, the obtained FeCoP@NCNFs displays good bifunctional electrocatalytic activity. In 1 M KOH, the FeCoP@NCNFs achieves 10 mA cm^?2 at an overpotential of 290, 226 mV for OER and HER, respectively. Moreover, it demands overpotential of 196 mV to achieve 10 mA cm^?2 for HER in 0.5 M H₂SO₄. The FeCoP@NCNFs is used as both anode and cathode for overall water splitting, it requires a low voltage of 1.65 V to achieve a current density of 10 mA cm^?2 and maintains outstanding stability over 10 h. Herein, a strategy for preparing bifunctional electrocatalysts of compositing transition metal phosphides with carbon nanofibers is proposed, and the application of metal-organic framework in electrocatalytic field is further extended.     

RhRu alloyed nanoparticles confined within metal organic frameworks for electrochemical hydrogen evolution at all pH values

As an effective way to generate high-purity hydrogen through water electrolysis, electrochemical hydrogen evolution reaction (HER) underpins various clean-energy technologies. Nevertheless, most of the currently reported HER catalysts only exhibited good activity in a narrow pH range (e. g. in acid electrolyte). Thence, developing high-performance electrocatalysts for HER at all pH values is significant and imperative. Herein, we report an active electrocatalyst of Rh_xRu_100-x@UiO-66-NH₂ (x denotes the initial atomic percentage of Rh in RhRu alloys) by in-situ confining RhRu binary alloys within metal-organic framework (MOF) of UiO-66-NH₂. Among the Rh_xRu_100-x@UiO-66-NH₂ samples, Rh₅₀Ru₅₀@UiO-66-NH₂ exhibited the most outstanding HER performance at all pH values, as well as comparable activity and outperformed stability to the commercial Ru/C and Pt/C catalysts. In HER tests, Rh₅₀Ru₅₀@UiO-66-NH₂ displayed an overpotential of 77 mV, 114 mV and 177 mV at the current density of 10 mA cm⁻² in 0.5 M H₂SO₄ (pH = 0.53), 1 M PBS (pH = 7) and 1 M KOH (pH = 14) solutions, respectively. The strategy for confining metal nanoparticles within the cavities of MOFs can enrich the toolbox for design and construction of low cost, efficient, and environment-friendly catalysts for hydrogen production toward clean energy applications.     

Carbon supported bifunctional Rh–Ni(OH)2/C nanocomposite catalysts with high electrocatalytic efficiency for alkaline hydrogen evolution reaction

Pt group metals display lower HER activity in alkaline solution than in acidic solution, because they are inefficient in the water dissociation step (Volmer step). Compared with Pt, the activity difference of Rh in alkaline and acidic media is much smaller. Meanwhile, Ni(OH)₂ is proved to be an effective catalyst for water dissociation. Therefore, Rh–Ni(OH)₂/C nanocomposites with different Rh:Ni(OH)₂ ratios were synthesized by a co-deposition/partial reduction method, and their microstructures as well as electrocatalytic properties were studied. The results show that Rh and Ni(OH)₂ display synergistic effect in Rh–Ni(OH)₂/C nanocomposites. The Rh–Ni(OH)₂/C nanocomposite with a molar ratio of Rh to Ni(OH)₂ of 1:1 exhibits the highest activity. It shows an overpotential of 36 mV at 10 mA cm^?2 and a Tafel slope of 32 mV dec^?1 for HER in alkaline media, which is superior to commercial Pt/C. In addition, the Rh–Ni(OH)₂/C (1:1) nanocomposite shows excellent durability in alkaline media as well.     

Metal and phosphonium-based ionic liquid: A new Co and P dual-source for synthesis of cobalt phosphide toward hydrogen evolution reaction

Phosphonium-based ionic liquid, containing cobalt ion, was applied as novel phosphorus and metal dual-source for fabrication of cobalt phosphide. Trihexyl(tetradecyl)phosphonium tetrachlorocobaltate(II) ([P_6,6,6,14]₂[CoCl₄]) with carbon nanotubes (CNTs) was utilized to obtain the Co₂P/CNTs via one step phosphidation. This material exhibits a good catalytic activity toward hydrogen evolution reaction (HER) including an onset overpotential of 85 mV, a Tafel slope of 47 mV dec⁻¹, current densities of 10 and 20 mA cm⁻² at overpotentials of 150 and 178 mV, and it has a good stability to keep the HER activity. All experimental results confirmed that [P_6,6,6,14]₂[CoCl₄] can form Co₂P without adding other reagent and CNTs can improve the electrical conductivity and contribute to the formation of cobalt phosphide.     

Quaternary-metal phosphide as electrocatalyst for efficient hydrogen evolution reaction in alkaline solution

Hydrogen evolution reaction (HER) is a critical process in electrocatalytic water splitting for hydrogen production. However, the development of low-cost electrocatalysts for highly efficient HER is still a huge challenge. Hence, we fabricate a multi-metal phosphide on Ni foam, FeCoNiNb_xP, through a facile hydrothermal reaction followed by phosphorization. We find that Nb promotes the formation of metal phosphides, and the main phases of the catalysts with Nb are multiphase phosphides. Importantly, the Nb incorporation significantly improves the HER activity of FeCoNiP. We show that FeCoNiNb_0.3P has the best HER activity, which only requires an overpotential of 78 mV to achieve a current density of 10 mA cm^?2 in 1 M KOH, and demonstrates excellent stability under both constant potential and varied current densities. Our findings show that the multiple-metal compounds are beneficial to the improvement of catalytic activity and provide guidance on the design of novel catalysts for applications.     

Boosting hydrogen evolution activity and durability of Pd–Ni–P nanocatalyst via crystalline degree and surface chemical state modulations

Developing efficient, durable, and economical electro-catalysts for large-scale commercialization of hydrogen evolution (HER) is still challenging. Herein, we report for the first time, to the best of our knowledge, a Pd-based ternary metal phosphide as an active and stable HER catalyst. The face-centered-cubic Pd–Ni–P nanoparticles (NPs) annealed at 400 °C show the best HER activity with a low overpotential of 32 mV to realize a current density of 10 mA cm⁻² and a high mass activity of 1.23 mA μg⁻¹_Pd, superior to Pd NPs, Pd–P NPs, Pd–Ni NPs, and Pd–Ni–P NPs annealed under different temperatures. Moreover, this catalyst is also highly stable during 20 h of continuous electrolysis. Notably, the easily fabricated Pd–Ni–P NPs are among the most active Pd-based HER catalysts. This work indicates that Pd-based metal phosphides could be potentially applied as a type of practical HER catalyst and might inform the fabrication of analogous materials for hydrogen-related applications.     

Heterostructured two dimensional materials of MXene and graphene by hydrothermal method for efficient hydrogen production and HER activities

Recent development on two-dimensional (2D) heterostructured graphene and MXene materials were explored for electrochemical water splitting hydrogen evolution reaction (HER) activity. The hybrid MXene/reduced graphene oxides as two-dimensional (2D) hybrid structures were prepared by facile hydrothermal techniques at 150 °C with MXene and RG hybrid layered composites. As-prepared electrocatalytic active materials have been confirmed through structural and surface morphological studies such as XRD, RAMAN, FT-IR and SEM analysis. The prepared 2D materials were carried out for HER activities due to attractive conductivity and mass transfer process. HER performance were tested from linear sweep voltammetry (LSV) cures. The prepared MX, RG and MX@RG hybrid electrocatalyst exhibited overpotential values as observed as 220 mV, 193 mV, 121 mV respectively at 10 mAcm^?2 cathodic on set. MX@RG hybrid heterostructure exhibited enhanced HER action with lowest overpotential (η = 121 mV) and good H₂ productions as an active future electrocatalyst for energy storage and conversion applications.     

Phosphorus-doping induced electronic modulation of CoS2–MoS2 hollow spheres on MoO2 film-Mo foil for synergistically boosting alkaline hydrogen evolution reaction

Combination of anionic doping and multicomponent synergism are effective approach to improve the performance of electrocatalysts toward hydrogen evolution reaction (HER) process. Herein, P-doped CoS₂–MoS₂ hollow spheres assembled by countless sheets on oxidized Mo foil (P–CoS₂/MoS₂/MoO₂) was synthesized by hydrothermal and phosphorization process. The unique hollow structure with countless sheets as wall endows more accessible active sites, fast electron/mass transport and high conductivity. P-doping could redistribute the local charge density and optimize the surface charge state to improve the intrinsic activity and accelerate reaction kinetics. The optimized P–CoS₂/MoS₂/MoO₂ exhibits an outstanding HER performance with an overpotential of 85 mV to reach 10 mA cm⁻², a small Tafel slope of 84.6 mV dec⁻¹, superior intrinsic HER activity and robust durability under alkaline solution. This work proposed a feasible strategy to build the hollow, heterostructured and binder-free electrode in renewable energy application.     

Structure-design and synthesis of nickel-cobalt oxide/sulfide/phosphide composite nanowire arrays for efficient overall water splitting

The construction of cost-effective bifunctional electrocatalysts with the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is significant for efficient overall water splitting. Herein, this work demonstrates a novel strategy for the synthesis of nickel-cobalt oxides/sulfides/phosphides composite (denoted as NiCoO–2P/S) nanoarrays on Ni foam. In this method, Ni–Co bimetallic oxide nanowires on Ni foam were partially phosphorized and sulfurized simultaneously in situ to yield Ni–Co oxide/sulfide/phosphide composite. The NiCoO–2P/S arrays have good interfacial effects and display many holes in the nanowires, giving it the advantage of large accessible surfaces on the nanowires and a beneficial for the release of gas bubbles, resulting in an excellent OER performance with a low overpotential (η) of 254 mV at 100 mA cm^?2 and good HER activity (η₁₀ = 143 mV at 10 mA cm^?2). The electrocatalytic test results demonstrate small Tafel slopes (82 mV dec^?1 for HER, 88 mV dec^?1 for OER) and the satisfying durability in an alkaline electrolyte, indicating that the HER and OER activity was enhanced by the introduction of the Ni/Co sulfides and phosphides into Ni–Co oxides composite nanowires. Furthermore, the as-prepared NiCoO–2P/S catalyst can be used as both the anode and the cathode simultaneously to realize overall water splitting in the two-electrode electrolyzer. This system can be driven at low cell voltages of 1.50 and 1.68 V to achieve current densities of 10 and 100 mA cm^?2, respectively. This work provides an alternative strategy to prepare high-performance bifunctional electrochemical materials and demonstrates the advantages of Ni–Co oxide/sulfide/phosphide composites for water splitting.     

Bamboo-like N-doped carbon tubes encapsulated Co2P–Fe2P derived from zeolitic imidazolate framework as an efficient trifunctional electrocatalyst for water splitting and Zn-air batteries

The development of high-performance and stable trifunctional electrocatalysts is a pressing challenge for the practical application of water splitting and regenerative Zn-air batteries. Herein, bamboo-like N-doped carbon tubes encapsulated Co₂P–Fe₂P nanoparticles (CoFe-PN/C) was fabricated via a facile template-sacrificial approach by using CoZn-ZIF trapping Fe³⁺ (CoFeZn/C) as the precursor. The incorporation of Fe³⁺ was achieved by the one-pot synthesis approach during crystallization of ZIF, which led to the generation of the unique bamboo-like tube structure under the condition of simultaneous phosphating and carbonization. Benefiting from the large surface area, the optimized electronic structure of active sites and the unique bamboo-like nanotube, the resultant CoFe-PN/C can be used as the trifunctional electrocatalyst possessing a small overpotential at 10 mA cm⁻² for the HER (178 mV) and OER (300 mV), as well as a high half-wave potential of 0.884 V for ORR (40 mV more positive than that of commercial 20 wt% Pt/C). Moreover, the self-designed CoFe-PN/C||CoFe-PN/C alkaline electrolyzer driving 50 mA cm⁻² only need operating potential of 1.84 V and the maximum discharge power density of the CoFe-PN/C-assembled ZABs could achieve 152.0 mW cm⁻², superior to those of Pt/RuO₂ couple. This work will facilitate the development and application of trifunctional electrocatalysts based on bi-transition metallic phosphides for energy conversion and storage technology.     

Partial phosphorization of porous Co–Ni–B for efficient hydrogen evolution electrocatalysis

Design of cost-effective and high-efficient electrocatalysts for hydrogen evolution reaction (HER) is of vital significance for the current renewable energy devices — fuel cells. Herein, we report a facile strategy to prepare partial phosphorization of Co–Ni–B material with porous structure via a water-bath boronizing and subsequent phosphorization process at moderate temperature. The optimal atomic proportion of Co to Ni is investigated via physical and electrochemical characterization. As a result, Co₉–Ni₁–B–P exhibits the best HER activity, which require an lower overpotential of ~192 mV to deliver a current density value of 10 mA cm⁻² and a smaller Tafel slope of 94 mV dec⁻¹ in alkaline media, relative to P-free Co–Ni–B catalysts, Co₉–Ni₁–B–P with other Co: Ni proportion and mono metallic borides The excellent electrocatalytic performance of Co₉–Ni₁–B–P is mainly ascribed to the three-dimensional (3D) porous structure and the coordinate functionalization between the borides and phosphides. This work provides a promising strategy for the exploration of quaternary composites as efficient and cost-effective electrocatalysts for HER.     

Heterogeneous cobalt phosphides nanoparticles anchored on carbon cloth realizing the efficient hydrogen generation reaction

Intrinsic activity modifying of electrocatalysts is crucial to realizing the excellent catalytic performance towards hydrogen evolution reaction. Herein, we demonstrate a highly efficient electrocatalyst based on heterogeneous cobalt phosphides nanoparticles. The ultrafine size of the as-prepared catalyst (∼5 nm) ensures the efficient extension of active sites. Furthermore, the incorporation of orthorhombic CoP and Co₂P contributes to the improvement of the inherent catalytic property. As a consequence, the as-prepared heterogeneous cobalt phosphides nanoparticles supported on carbon cloth exhibit impressive electrocatalytic activity, which only acquire a small overpotential of 90 mV at a current density of 10 mA cm⁻², and present a low Tafel slope (67.9 mV dec⁻¹), a large exchange current density (0.58 mA cm⁻²) as well as good durability. Therefore, this work provides a favorable guidance for exploring executable strategies to improve catalyst activity.     

One-step fabrication of heterostructured CoNi-LDH@NiCo alloy for effective alkaline hydrogen evolution

Construction of heterostructured electrocatalyst with interface effect is an effective strategy for enhancing the alkaline hydrogen evolution efficiency, whereas this process often requires complex treatments. Herein, we proposed a one-step electrodeposition method to obtain heterostructured CoNi-LDH@NiCo alloy on Ni foam (NF) through a competition reduction between NO₃^? group and metal cations in the electrolyte. The HER performance for the CoNi-LDH@NiCo alloy achieved the current density of 10 mA cm^?2 at overpotential of 69 mV in 1 M KOH solution, improved 60% for η₁₀ by comparing with the pristine NiCo alloy. Utilizing the specialized adsorption of CoNi-LDH for H₂O and the featured attractiveness of NiCo alloy for H atom, the interface effect of the heterostructure electrocatalyst accelerated the dissociation of water molecules and elevated the catalytic kinetics dramatically. This work points out a potential approach towards the easy construction of inexpensive heterostructured electrocatalysts for HER activity in alkaline medium.     

Facile construction of porous and heterostructured molybdenum nitride/carbide nanobelt arrays for large current hydrogen evolution reaction

The development of cost-effective, highly efficient and stable electrocatalysts for alkaline water electrolysis at a large current density has attracted considerable attention. Herein, we reported a one-dimensional (1D) porous Mo₂C/Mo₂N heterostructured electrocatalyst on carbon cloth as robust electrode for large current hydrogen evolution reaction (HER). The MoO₃ nanobelt arrays and urea were used as the metal and non-metal sources to fabricate the electrocatalyst by one-step thermal reaction. Due to the in-situ formed abundant high active interfaces and porous structure, the Mo₂C/Mo₂N electrocatalyst shows enhanced HER activity and kinetics, as exemplified by low overpotentials of 54, 73, and 96 mV at a current density of 10 mA cm^?2 and small Tafel slopes of 48, 59 and 60 mV dec^?1 in alkaline, neutral and acid media, respectively. Furthermore, the optimal Mo₂C/Mo₂N catalyst only requires a low overpotential of 290 mV to reach a large current density of 500 mA cm^?2 in alkaline media, which is superior to commercial Pt/C catalyst (368 mV) and better than those of recently reported Mo-based electrocatalysts. This work paves a facile strategy to construct highly efficient and low-cost electrocatalyst for water splitting, which could be extended to fabricate other heterostructured electrocatalyst for electrocatalysis and energy conversion.     

Ruthenium-manganese phosphide nanohybrid supported on graphene for efficient hydrogen evolution reaction in acid and alkaline conditions

Transition metal phosphides (TMPs) have been proved to be promising, economical and effective catalysts for hydrogen evolution reaction (HER). Precious metals with transition metals alloying can appropriately adjust the adsorption energy, which is an effective solution for greatly reducing the cost of noble metal catalysts and improving their inherent performance. Herein, a simple method was employed to synthesize MnRuPOGO-500 nano-catalysts with a particle size of about 5 nm, which showed excellent HER performance under both acid and basic media. In acidic solution, the optimal catalyst displayed the overpotential of HER to reach 10 mA cm^?2 with 109 mV, a small Tafel slope of 38.55 mV dec^?1 and long-time durability of 60 h. Especially in alkaline medium, the low overvoltage of 27 mV, a small Tafel slope of 57.35 mV dec^?1 and continuing stability of 48 h were further achieved. Meanwhile, we can find that manganese has negligible HER activity, but the doping of manganese generates a synergistic modulation effect in the MnP–Ru₂P alloy, thereby improving the HER performance of the catalyst. This paper brings a simple scheme and unique insights to the design of transition metals and platinum group metals (PGMs) phosphide alloy electrocatalysts.