Concave Structural Carbon Co-Doped with Iron Atom Pairs and Nitrogen as Ultra-High Performance Catalyst Toward Oxygen Reduction.

It is crucial to rationally design and synthesize atomic-scale transition metal-doped carbon catalysts with high electrocatalytic activity to achieve a high-efficient oxygen reduction reaction (ORR). Herein, an electrocatalyst comprised of Fe-Fe dual atom pairs and N-doped concave carbon are reported (N-CC@Fe DA) that achieves ultrahigh electrocatalytic ORR activity. The catalyst is prepared by a gaseous doping approach, with zeolitic imidazolate framework-8 (ZIF-8) as the carbon framework precursor and cyclopentadienyliron dicarbonyl dimer as the Fe-Fe atom pair precursor. The catalyst exhibits high cathodic ORR catalytic performance in an alkaline Zn/air battery and proton exchange membrane fuel cell (PEMFC), yielding peak power densities of 241 mW cm-2 and 724 mW cm-2, respectively, compared to 127 mW cm-2 and 1.20 W cm-2 with conventional Pt/C catalysts as cathodes. The presence of Fe atom pairs coordinate with N atoms is revealed by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analysis, and Density Functional Theory (DFT) calculation results show that the Fe-Fe pair structure is beneficial for adsorbing oxygen molecules, activating the O─O bond, and desorbing OH* intermediates formed during oxygen reduction, resulting in a more efficient oxygen reaction. The findings may provide a new pathway for preparing ultra-high-performance doped carbon catalysts with Fe-Fe atom pair structures.

Tuning Active Metal Atomic Spacing by Filling of Light Atoms and Resulting Reversed Hydrogen Adsorption-Distance Relationship for Efficient Catalysis.

Precisely tuning the spacing of the active centers on the atomic scale is of great significance to improve the catalytic activity and deepen the understanding of the catalytic mechanism, but still remains a challenge. Here, we develop a strategy to dilute catalytically active metal interatomic spacing (dM-M) with light atoms and discover the unusual adsorption patterns. For example, by elevating the content of boron as interstitial atoms, the atomic spacing of osmium (dOs-Os) gradually increases from 2.73 to 2.96 Å. More importantly, we find that, with the increase in dOs-Os, the hydrogen adsorption-distance relationship is reversed via downshifting d-band states, which breaks the traditional cognition, thereby optimizing the H adsorption and H2O dissociation on the electrode surface during the catalytic process; this finally leads to a nearly linear increase in hydrogen evolution reaction activity. Namely, the maximum dOs-Os of 2.96 Å presents the optimal HER activity (8 mV @ 10 mA cm-2) in alkaline media as well as suppressed O adsorption and thus promoted stability. It is believed that this novel atomic-level distance modulation strategy of catalytic sites and the reversed hydrogen adsorption-distance relationship can shew new insights for optimal design of highly efficient catalysts.

Work-function-induced Interfacial Built-in Electric Fields in Os-OsSe2 Heterostructures for Active Acidic and Alkaline Hydrogen Evolution.

Theoretical calculations unveil that the formation of Os-OsSe2 heterostructures with neutralized work function (WF) perfectly balances the electronic state between strong (Os) and weak (OsSe2 ) adsorbents and bidirectionally optimizes the hydrogen evolution reaction (HER) activity of Os sites, significantly reducing thermodynamic energy barrier and accelerating kinetics process. Then, heterostructural Os-OsSe2 is constructed for the first time by a molten salt method and confirmed by in-depth structural characterization. Impressively, due to highly active sites endowed by the charge balance effect, Os-OsSe2 exhibits ultra-low overpotentials for HER in both acidic (26 mV @ 10 mA cm-2 ) and alkaline (23 mV @ 10 mA cm-2 ) media, surpassing commercial Pt catalysts. Moreover, the solar-to-hydrogen device assembled with Os-OsSe2 further highlights its potential application prospects. Profoundly, this special heterostructure provides a new model for rational selection of heterocomponents.

Ultra-Fast and In-Depth Reconstruction of Transition Metal Fluorides in Electrocatalytic Hydrogen Evolution Processes.

Hitherto, there are almost no reports on the complete reconstruction in hydrogen evolution reaction (HER). Herein, the authors develop a new type of reconfigurable fluoride (such as CoF2 ) pre-catalysts, with ultra-fast and in-depth self-reconstruction, substantially promoting HER activity. By experiments and density functional theory (DFT) calculations, the unique surface structure of fluorides, alkaline electrolyte and bias voltage are identified as key factors for complete reconstruction during HER. The enrichment of F atoms on surface of fluorides provides the feasibility of spontaneous and continuous reconstruction. The alkaline electrolyte triggers rapid F- leaching and supplies an immediate complement of OH- to form amorphous α-Co(OH)2 which rapidly transforms into ß-Co(OH)2 . The bias voltage promotes amorphous crystallization and accelerates the reconstruction process. These endow the generation of mono-component and crystalline ß-Co(OH)2 with a loose and defective structure, leading to an ultra-low overpotential of 54 mV at 10 mA cm-2 and super long-term stability exceeding that of Pt/C. Moreover, DFT calculations confirm that F- leaching optimizes hydrogen and water adsorption energies, boosting HER kinetics. Impressively, the self-reconstruction is also applicable to other non-noble transition metal fluorides. The work builds the fundamental comprehension of complete self-reconstruction during HER and provides a new perspective to conceive advanced catalysts.

Nanostructured Metal Borides for Energy-Related Electrocatalysis: Recent Progress, Challenges, and Perspectives.

The discovery of durable, active, and affordable electrocatalysts for energy-related catalytic applications plays a crucial role in the advancement of energy conversion and storage technologies to achieve a sustainable energy future. Transition metal borides (TMBs), with variable compositions and structures, present a number of interesting features including coordinated electronic structures, high conductivity, abundant natural reserves, and configurable physicochemical properties. Therefore, TMBs provide a wide range of opportunities for the development of multifunctional catalysts with high performance and long durability. This review first summarizes the typical structural and electronic features of TMBs. Subsequently, the various synthetic methods used thus far to prepare nanostructured TMBs are listed. Furthermore, advances in emerging TMB-catalyzed reactions (both theoretical and experimental) are highlighted, including the hydrogen evolution reaction, the oxygen evolution reaction, the oxygen reduction reaction, the carbon dioxide reduction reaction, the nitrogen reduction reaction, the methanol oxidation reaction, and the formic acid oxidation reaction. Finally, challenges facing the development of TMB electrocatalysts are discussed, with focus on synthesis and energy-related catalytic applications, and some potential strategies/perspectives are suggested as well, which will profit the design of more efficient TMB materials for application in future energy conversion and storage devices.

Molybdenum Carbide-PtCu Nanoalloy Heterostructures on MOF-Derived Carbon toward Efficient Hydrogen Evolution.

In this study, PtCu-Mo2 C heterostructure with charge redistribution is investigated via first-principles theoretical calculations. Mo2 C can promote the formation of the electron-rich region of PtCu as an active site, displaying an optimized adsorption behavior toward hydrogen in terms of reduced thermodynamic energy barriers. Owing to the attractive density functional theory calculation results, the PtCu-Mo2 C heterostructure is fabricated via carbonization of the unique metal-organic framework (MOF) followed by the replacement reduction reaction for the first time. Owing to its swift kinetics and outstanding specific activity, it exhibits high hydrogen evolution reaction (HER) catalytic activity (26 mV @ 10 mA cm-2 ) and superior mass activity (1 A mgPt -1 at -0.04 V) in acidic media, which is approximately six times that of commercial Pt/C catalysts. The perception of the intrinsic activity origin of the alloy with an excellent structural support can guide the development of Pt-based and other alloy catalysts in future.

Electrocatalytic Oxygen Evolution Reaction in Acidic Conditions: Recent Progress and Perspectives.

The electrochemical oxygen evolution reaction (OER) is an important half-cell reaction in many renewable energy conversion and storage technologies, including electrolyzers, nitrogen fixation, CO2 reduction, metal-air batteries, and regenerative fuel cells. Among them, proton exchange membrane (PEM)-based devices exhibit a series of advantages, such as excellent proton conductivity, high durability, and good mechanical strength, and have attracted global interest as a green energy device for transport and stationary sectors. Nevertheless, with a view to rapid commercialization, it is urgent to develop highly active and acid-stable OER catalysts for PEM-based devices. In this Review, based on the recent advances in theoretical calculation and in situ/operando characterization, the OER mechanism in acidic conditions is first discussed in detail. Subsequently, recent advances in the development of several types of acid-stable OER catalysts, including noble metals, non-noble metals, and even metal-free OER materials, are systematically summarized. Finally, the current key issues and future challenges for materials used as acidic OER catalysis are identified and potential future directions are proposed.

Anion Modulation of Pt-Group Metals and Electrocatalysis Applications.

Pt-group metal (PGM) electrocatalysts with unique electronic structures and irreplaceable comprehensive properties play crucial roles in electrocatalysis. Anion engineering can create a series of PGM compounds (such as RuP2 , IrP2 , PtP2 , RuB2 , Ru2 B3 , RuS2 , etc.) that provide a promising prospect for improving the electrocatalytic performance and use of Pt-group noble metals. This review seeks the electrochemical activity origin of anion-modulated PGM compounds, and systematically analyzes and summarizes their synthetic strategies and energy-relevant applications in electrocatalysis. Orientation towards the sustainable development of nonfossil resources has stimulated a blossoming interest in the design of advanced electrocatalysts for clean energy conversion. The anion-modulated strategy for Pt-group metals (PGMs) by means of anion engineering possesses high flexibility to regulate the electronic structure, providing a promising prospect for constructing electrocatalysts with superior activity and stability to satisfy a future green electrochemical energy conversion system. Based on the previous work of our group and others, this review summarizes the up-to-date progress on anion-modulated PGM compounds (such as RuP2 , IrP2 , PtP2 , RuB2 , Ru2 B3 , RuS2 , etc.) in energy-related electrocatalysis from the origin of their activity and synthetic strategies to electrochemical applications including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), N2 reduction reaction (NRR), and CO2 reduction reaction (CO2 RR). At the end, the key problems, countermeasures and future development orientations of anion-modulated PGM compounds toward electrocatalytic applications are proposed.

Anion-Modulated Platinum for High-Performance Multifunctional Electrocatalysis toward HER, HOR, and ORR.

Efficient electrocatalyst toward hydrogen evolution/oxidation reactions (HER/HOR) and oxygen reduction reaction (ORR) is desirable for water splitting, fuel cells, etc. Herein, we report an advanced platinum phosphide (PtP2) material with only 3.5 wt % Pt loading embedded in phosphorus and nitrogen dual-doped carbon (PNC) layer (PtP2@PNC). The obtained catalyst exhibits robust HER, HOR, and ORR performance. For the HER, a much low overpotential of 8 mV is required to achieve the current density of 10 mA cm-2 compared with Pt/C (22 mV). For the HOR, its mass activity (MA) at an overpotential of 40 mV is 2.3-fold over that of the Pt/C catalyst. Interestingly, PtP2@PNC also shows exceptional ORR MA which is 2.6 times higher than that of Pt/C and has robust stability in alkaline solutions. Undoubtedly, this work reveals that PtP2@PNC can be employed as nanocatalysts with an impressive catalytic activity and stability for broad applications in electrocatalysis.

Synergistic Coupling of Ni Nanoparticles with Ni3 C Nanosheets for Highly Efficient Overall Water Splitting.

Exploring earth-abundant bifunctional electrocatalysts with high efficiency for water electrolysis is extremely demanding and challenging. Herein, density functional theory (DFT) predictions reveal that coupling Ni with Ni3 C can not only facilitate the oxygen evolution reaction (OER) kinetics, but also optimize the hydrogen adsorption and water adsorption energies. Experimentally, a facile strategy is designed to in situ fabricate Ni3 C nanosheets on carbon cloth (CC), and simultaneously couple with Ni nanoparticles, resulting in the formation of an integrated heterostructure catalyst (Ni-Ni3 C/CC). Benefiting from the superior intrinsic activity as well as the abundant active sites, the Ni-Ni3 C/CC electrode demonstrates excellent bifunctional electrocatalytic activities toward the OER and hydrogen evolution reaction (HER), which are superior to all the documented Ni3 C-based electrocatalysts in alkaline electrolytes. Specifically, the Ni-Ni3 C/CC catalyst exhibits the low overpotentials of only 299 mV at the current density of 20 mA cm-2 for the OER and 98 mV at 10 mA cm-2 for the HER in 1 m KOH. Furthermore, the bifunctional Ni-Ni3 C/CC catalyst can propel water electrolysis with excellent activity and nearly 100% faradic efficiency. This work highlights an easy approach for designing and constructing advanced nickel carbide-based catalysts with high activity based on the theoretical predictions.

Versatile Route To Fabricate Precious-Metal Phosphide Electrocatalyst for Acid-Stable Hydrogen Oxidation and Evolution Reactions.

Highly active catalyst for the hydrogen oxidation/evolution reactions (HOR and HER) plays an essential role for the water-to-hydrogen reversible conversion. Currently, increasing attention has been concentrated on developing low-cost, high-activity, and long-life catalytic materials, especially for acid media due to the promise of proton exchange membrane (PEM)-based electrolyzers and polymer electrolyte fuel cells. Although non-precious-metal phosphide (NPMP) catalysts have been widely researched, their electrocatalytic activity toward HER is still not satisfactory compared to that of Pt catalysts. Herein, a series of precious-metal phosphides (PMPs) supported on graphene (rGO), including IrP2-rGO, Rh2P-rGO, RuP-rGO, and Pd3P-rGO, are prepared by a simple, facile, eco-friendly, and scalable approach. As an example, the resultant IrP2-rGO displays better HER electrocatalytic performance and longer durability than the benchmark materials of commercial Pt/C under acidic, neutral, and basic electrolytes. To attain a current density of 10 mA cm-2, IrP2-rGO shows overpotentials of 8, 51, and 13 mV in 0.5 M dilute sulfuric acid, 1.0 M phosphate-buffered saline (PBS), and 1.0 M potassium hydroxide solutions, respectively. Additionally, IrP2-rGO also exhibits exceptional HOR performance in the 0.1 M HClO4 medium. Therefore, this work offers a vital addition to the development of a number of PMPs with excellent activity toward HOR and HER.

Single-Atom Catalysts for Electrochemical Hydrogen Evolution Reaction: Recent Advances and Future Perspectives.

Hydrogen, a renewable and outstanding energy carrier with zero carbon dioxide emission, is regarded as the best alternative to fossil fuels. The most preferred route to large-scale production of hydrogen is by water electrolysis from the intermittent sources (e.g., wind, solar, hydro, and tidal energy). However, the efficiency of water electrolysis is very much dependent on the activity of electrocatalysts. Thus, designing high-effective, stable, and cheap materials for hydrogen evolution reaction (HER) could have a substantial impact on renewable energy technologies. Recently, single-atom catalysts (SACs) have emerged as a new frontier in catalysis science, because SACs have maximum atom-utilization efficiency and excellent catalytic reaction activity. Various synthesis methods and analytical techniques have been adopted to prepare and characterize these SACs. In this review, we discuss recent progress on SACs synthesis, characterization methods, and their catalytic applications. Particularly, we highlight their unique electrochemical characteristics toward HER. Finally, the current key challenges in SACs for HER are pointed out and some potential directions are proposed as well.

UIO-66-NH2-derived mesoporous carbon used as a high-performance anode for the potassium-ion battery.

As potassium is abundant and has an electronic potential similar to lithium's, potassium-ion batteries (KIBs) are considered as prospective alternatives to lithium-ion batteries (LIBs). However, the much larger radius of the K ion poses challenges for the potassiation and depotassiation processes when the typical graphite-based anode is used, resulting in poor electrochemical performance. Thus, there is an urgent need to develop novel anode materials that are suitable for K ions. Herein, we develop a porous carbon material with high surface area derived from UIO-66-NH2 metal-organic frameworks as an anode material instead of a graphite-based anode. The material is prepared using a double-solvent diffusion-pyrolysis method, which increased mesopore volume and average pore size, and to a certain extent, slightly improved the nitrogen content of the production. The material exhibits a high capacity as well as excellent rate performance and cycling stability. A potassium battery with our porous carbon as the anode delivers a high reversible capacity of 346 mA h g-1 at 100 mA g-1 (compared to 279 mA h g-1 with a graphite-based anode), and 214 mA h g-1 at a discharge rate of up to 2 A g-1. After 800 cycles, the capacity is still 187 mA h g-1 at 0.1 A g-1. Qualitative and quantitative kinetics analyses demonstrated that the battery's high K storage performance was principally dominated by a surface-driven capacitive mechanism, and the potassiation and depotassiation processes may have occurred on the surface of the porous carbon instead of in the interlayer space, as is the case with a graphite anode. This work may provide a basis for developing other carbonaceous materials to use in KIBs.

Double Metal Diphosphide Pair Nanocages Coupled with P-Doped Carbon for Accelerated Oxygen and Hydrogen Evolution Kinetics.

Developing efficient and durable bifunctional transition metal phosphide (TMP) electrocatalysts is still a great challenge because of its relatively sluggish kinetics of oxygen evolution reaction (OER). Herein, we report a unique bimetallic diphosphide pair (FeP2-NiP2) forming spherical nanocages encapsulated in P-doped carbon layers (FeP2-NiP2@PC) as advanced bifunctional electrocatalyst synthesized by a very facile phosphorization approach. The obtained FeP2-NiP2@PC electrocatalyst exhibits an outstanding OER activity with an ultralow overpotential of 248 mV in 1 M KOH and a low overpotential of 117 mV for HER in 0.5 M H2SO4 (@10 mA·cm-2). Also it gives an exceptional long-term durability toward OER (60 h) and HER (20 h). Differently from the electrocatalysts as reported, after successive 3000 cycles CV acceleration, its overpotential decreases about 10 mV. Further investigation unveils that the electrochemical activation process boosts in situ phase transformation of oxides and phosphides to oxyhydroxides as the vital intermediates in FeP2-NiP2@PC during OER electrocatalysis. The direct observation of vital intermediates has been rarely reported on Fe/Ni-based phosphide electrocatalysts. Our exploration demonstrates an extraordinarily efficient and stable nonprecious TMP bifunctional electrocatalyst and provides a novel prospect to shed light on the intrinsic OER electrocatalytic behavior of Fe/Ni-based phosphide electrocatalysts.

Phosphorization engineering ameliorated the electrocatalytic activity for overall water splitting on Ni3S2 nanosheets.

Phosphorization engineering is an alternative method to explore highly efficient electrocatalysts for water splitting. Herein, a heterostructure consisting of Ni2P and Ni3S2 supported on commercial nickel foam (Ni3S2-Ni2P/NF) was prepared through the conversion of some Ni3S2 molecules into Ni2P by phosphorization engineering. Electrochemical tests revealed that the partial phosphorization of Ni3S2 effectively enhanced the catalytic activity of the host electrocatalyst towards the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in 1 M KOH; in particular, the Ni3S2-Ni2P/NF electrode exhibited the current density of 50 mA cm-2 at the very low OER overpotential of 287 mV and needed the low overpotential of 130 mV to afford 10 mA cm-2 for the HER. Moreover, the alkaline electrolyzer assembled by two Ni3S2-Ni2P/NF electrodes could deliver 10 mA cm-2 at the low voltage of 1.58 V and exhibited excellent durability during electrolysis for 15 h. Therefore, our study opens up an attractive fabrication strategy for highly active heterostructure electrocatalysts.

Realizing the extraction of carbon from WC for in situ formation of W/WC heterostructures with efficient photoelectrochemical hydrogen evolution.

Although extracting carbon atoms from carbides, as the reverse route to carbide derived carbon (CDC), may have more potentials for constructing advanced nanostructures, it has not been realized yet. As a proof of concept, in this work we realize the extraction of carbon atoms from carbide lattices by rationally controlling the reaction between carbides and Cl2. Thus, a homologous metallic W layer adhered on a WC (W/WC) heterostructure is created. Based on experimental results, such a W/WC heterostructure can be used as an efficient catalyst for the photoelectrocatalytic hydrogen evolution reaction (HER), where the photocurrent density at 0 V can reach up to 16 mA cm-2. Our theoretical calculations disclose that the Mott-Schottky effect accelerates electron flow across the interfaces and significantly decreases the work function of the W facet, which leads to excellent photoelectrocatalytic HER activity on the W facets. The presented results have broad implications since they demonstrate the generic capability to build homologous M/TMC heterostructures.

Activating rhodium phosphide-based catalysts for the pH-universal hydrogen evolution reaction.

Highly active and stable Pt-free electrocatalysts for hydrogen production via water splitting are of great demand for future energy systems. Herein, we report a novel hydrogen evolution reaction (HER) catalyst consisting of rhodium phosphide (Rh2P) nanoparticles as the core and N-doped carbon (NC) as the shell (Rh2P@NC). In a wide pH range, our catalyst not only possesses a small overpotential at 10 mA cm-2 (∼9 mV in 0.5 M H2SO4, ∼46 mV in 1.0 M PBS and ∼10 mV in 1.0 M KOH), but also demonstrates high stability. Importantly, all these performances are far superior to commercial Pt/C catalysts for HER. To the best of our knowledge, this is the highest HER performance reported so far in acidic and basic media. Density functional theory (DFT) calculations reveal that the introduction of phosphorus can significantly lower the proton adsorption energy of Rh/NC, thereby benefiting surface hydrogen generation. Moreover, this synthetic strategy for Rh2P@NC is also applied to other transition metal phosphides (TMPs)/nitrogen-doped carbon heterostructures (such as Ru2P@NC, Fe2P@NC, WP@NC etc.) with advanced performance toward HER and beyond.

Ultrahigh Conductive Copper/Large Flake Size Graphene Heterostructure Thin-Film with Remarkable Electromagnetic Interference Shielding Effectiveness.

To guarantee the normal operation of next generation portable electronics and wearable devices, together with avoiding electromagnetic wave pollution, it is urgent to find a material possessing flexibility, ultrahigh conductive, and superb electromagnetic interference shielding effectiveness (EMI SE) simultaneously. In this work, inspired by a building bricks toy with the interlock system, we design and fabricate a copper/large flake size graphene (Cu/LG) composite thin film (≈8.8 µm) in the light of high temperature annealing of a large flake size graphene oxide film followed by magnetron sputtering of copper. The obtained Cu/LG thin-film shows ultrahigh thermal conductivity of over 1932.73 (±63.07) W m-1 K-1 and excellent electrical conductivity of 5.88 (±0.29) × 106 S m-1 . Significantly, it also exhibits a remarkably high EMI SE of over 52 dB at the frequency of 1-18 GHz. The largest EMI SE value of 63.29 dB, accorded at 1 GHz, is enough to obstruct and absorb 99.99995% of incident radiation. To the best of knowledge, this is the highest EMI SE performance reported so far in such thin thickness of graphene-based materials. These outstanding properties make Cu/LG film a promising alternative building block for power electronics, microprocessors, and flexible electronics.

Co2P quantum dot embedded N, P dual-doped carbon self-supported electrodes with flexible and binder-free properties for efficient hydrogen evolution reactions.

Transition metal phosphides (TMPs) are considered to be superb catalysts for water splitting. In this work, we introduce an efficient strategy to fabricate dicobalt phosphide (Co2P) quantum dots embedded in N, P dual-doped carbon (Co2P@NPC) on carbon cloth (Co2P@NPC/CC) by in situ carbonization of cobalt ion induced phytic acid (PA) and polyaniline (PANI) macromolecule precursors. As a highly efficient self-supported electrode, it has a low onset overpotential (74 mV at 1 mA cm-2) approaching that of the commercial Pt/C catalyst for the hydrogen evolution reaction (HER) in acidic media. Meanwhile, it also shows very low overpotentials of only 116 and 129 mV at 10 mA cm-2 with robust stability in acidic and alkaline media, respectively.

RuP2 -Based Catalysts with Platinum-like Activity and Higher Durability for the Hydrogen Evolution Reaction at All pH†Values.

Highly active, stable, and cheap Pt-free catalysts for the hydrogen evolution reaction (HER) are under increasing demand for future energy conversion systems. However, developing HER electrocatalysts with Pt-like activity that can function at all pH values still remains as a great challenge. Herein, based on our theoretical predictions, we design and synthesize a novel N,P dual-doped carbon-encapsulated ruthenium diphosphide (RuP2 @NPC) nanoparticle electrocatalyst for HER. Electrochemical tests reveal that, compared with the Pt/C catalyst, RuP2 @NPC not only has Pt-like HER activity with small overpotentials at 10 mA cm-2 (38 mV in 0.5 m H2 SO4 , 57 mV in 1.0 m PBS and 52 mV in 1.0 m KOH), but demonstrates superior stability at all pH values, as well as 100 % Faradaic yields. Therefore, this work adds to the growing family of transition-metal phosphides/heteroatom-doped carbon heterostructures with advanced performance in HER.