Graphene Nanoarchitectonics: Recent Advances in Graphene‐Based Electrocatalysts for Hydrogen Evolution Reaction

Under the double pressures of both the energy crisis and environmental pollution, the exploitation and utilization of hydrogen, a clean and renewable power resource, has become an important trend in the development of sustainable energy‐production and energy‐consumption systems. In this regard, the electrocatalytic hydrogen evolution reaction (HER) provides an efficient and clean pathway for the mass production of hydrogen fuel and has motivated the design and construction of highly active HER electrocatalysts of an acceptable cost. In particular, graphene‐based electrocatalysts commonly exhibit an enhanced HER performance owing to their distinctive structural merits, including a large surface area, high electrical conductivity, and good chemical stability. Considering the rapidly growing research enthusiasm for this topic over the last several years, herein, a panoramic review of recent advances in graphene‐based electrocatalysts is presented, covering various advanced synthetic strategies, microstructural characterizations, and the applications of such materials in HER electrocatalysis. Lastly, future perspectives on the challenges and opportunities awaiting this emerging field are proposed and discussed.     

Polyaniline Derived N‐Doped Carbon‐Coated Cobalt Phosphide Nanoparticles Deposited on N‐Doped Graphene as an Efficient Electrocatalyst for Hydrogen Evolution Reaction

The development of highly efficient and durable non‐noble metal electrocatalysts for the hydrogen evolution reaction (HER) is significant for clean and renewable energy research. This work reports the synthesis of N‐doped graphene nanosheets supported N‐doped carbon coated cobalt phosphide (CoP) nanoparticles via a pyrolysis and a subsequent phosphating process by using polyaniline. The obtained electrocatalyst exhibits excellent electrochemical activity for HER with a small overpotential of ?135 mV at 10 mA cm^?2 and a low Tafel slope of 59.3 mV dec^?1 in 0.5 m H₂SO₄. Additionally, the encapsulation of N‐doped carbon shell prevents CoP nanoparticles from corrosion, exhibiting good stability after 14 h operation. Moreover, the as‐prepared electrocatalyst also shows outstanding activity and stability in basic and neutral electrolytes.     

Carbon‐Encapsulated WOx Hybrids as Efficient Catalysts for Hydrogen Evolution

Developing non‐noble metal catalysts as Pt substitutes, with good activity and stability, remains a great challenge for cost‐effective electrochemical evolution of hydrogen. Herein, carbon‐encapsulated WO_x anchored on a carbon support (WO_x@C/C) that has remarkable Pt‐like catalytic behavior for the hydrogen evolution reaction (HER) is reported. Theoretical calculations reveal that carbon encapsulation improves the conductivity, acting as an electron acceptor/donor, and also modifies the Gibbs free energy of H* values for different adsorption sites (carbon atoms over the W atom, O atom, W? O bond, and hollow sites). Experimental results confirm that WO_x@C/C obtained at 900 °C with 40 wt% metal loading has excellent HER activity regarding its Tafel slope and overpotential at 10 and 60 mA cm^?2, and also has outstanding stability at ?50 mV for 18 h. Overall, the results and facile synthesis method offer an exciting avenue for the design of cost‐effective catalysts for scalable hydrogen generation.     

Carbon‐Quantum‐Dots‐Loaded Ruthenium Nanoparticles as an Efficient Electrocatalyst for Hydrogen Production in Alkaline Media

Highly active, stable, and cheap Pt‐free catalysts for the hydrogen evolution reaction (HER) are facing increasing demand as a result of their potential use in future energy‐conversion systems. However, the development of HER electrocatalysts with Pt‐like or even superior activity, in particular ones that can function under alkaline conditions, remains a significant challenge. Here, the synthesis of a novel carbon‐loaded ruthenium nanoparticle electrocatalyst (Ru@CQDs) for the HER, using carbon quantum dots (CQDs), is reported. Electrochemical tests reveal that, even under extremely alkaline conditions (1 m KOH), the as‐formed Ru@CQDs exhibits excellent catalytic behavior with an onset overpotential of 0 mV, a Tafel slope of 47 mV decade^?1, and good durability. Most importantly, it only requires an overpotential of 10 mV to achieve the current density of 10 mA cm^?2. Such catalytic characteristics are superior to the current commercial Pt/C and most noble metals, non‐noble metals, and nonmetallic catalysts under basic conditions. These findings open a new field for the application of CQDs and add to the growing family of metal@CQDs with high HER performance.     

Co Nanoparticles Confined in 3D Nitrogen‐Doped Porous Carbon Foams as Bifunctional Electrocatalysts for Long‐Life Rechargeable Zn–Air Batteries

Proper design and simple preparation of nonnoble bifunctional electrocatalysts with high cost performance and strong durability for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is highly demanded but still full of enormous challenges. In this work, a spontaneous gas‐foaming strategy is presented to synthesize cobalt nanoparticles confined in 3D nitrogen‐doped porous carbon foams (CoNCF) by simply carbonizing the mixture of citric acid, NH₄Cl, and Co(NO₃)₂·6H₂O. Thanks to its particular 3D porous foam architecture, ultrahigh specific surface area (1641 m² g^?1), and homogeneous distribution of active sites (C–N, Co–N_x, and Co–O moieties), the optimized CoNCF‐1000‐80 (carbonized at 1000 °C, containing 80 mg Co(NO₃)₂·6H₂O in precursors) catalyst exhibits a remarkable bifunctional activity and long‐term durability toward both ORR and OER. Its bifunctional activity parameter (ΔE) is as low as 0.84 V, which is much smaller than that of noble metal catalyst and comparable to state‐of‐the‐art bifunctional catalysts. When worked as an air electrode catalyst in rechargeable Zn–air batteries, a high energy density (797 Wh kg^?1), a low charge/discharge voltage gap (0.75 V), and a long‐term cycle stability (over 166 h) are achieved at 10 mA cm^?2.     

碳基硫化钼电催化制氢催化剂的研究进展

金属铂是目前最高效的电催化制氢催化剂,但由于铂存在高成本、低储量等缺点,难以适合广泛的工业应用。因此,寻找低成本、高储量的替代电催化制氢催化剂成为未来发展的方向。二硫化钼因具有制氢活性较高、储量丰富、易于制备等优势越来越受到关注。二硫化钼的制氢活性主要取决于暴露的催化活性位数量和导电性。因此,利用纳米碳材料的高导电性和高比表面积来提高二硫化钼的导电性和制氢催化活性位的数量,是制备高活性二硫化钼电催化剂的重要策略之一。重点介绍了二硫化钼电催化制氢的基本原理,以及采用不同碳材料,如石墨烯、氧化石墨烯、碳纳米管等,改进二硫化钼电催化制氢性能的合成方法、催化效果及反应机理。最后,展望了利用碳材料辅助制备高活性、低成本电催化制氢催化剂的前景。     

稀土铈对镍-钴-磷合金电极的析氢催化性能的影响

采用自行研制的复合配合剂,用化学沉积法在酸性体系中制备了Ni-Co-P和Ni-Co-P稀土合金电极.研究了稀土元素铈对Ni-Co-P合金电极的析氢电催化活性和电化学稳定性的影响.通过电化学方法测定合金电极在7 mol/L KOH溶液中的阴极极化曲线、Tafel曲线和电化学稳定性曲线,结果表明,与Ni-Co-P合金电极相比,Ni-Co-P(RE)合金电极的析氢电位正移约90 mV,Ni-Co-P(RE)合金电极具有较优的析氢电催化活性和电化学稳定性.此外,还通过X射线衍射、扫描电镜和合金镀层成分分析,结果表明,稀土元素铈的加入使非晶态Ni-Co-P合金镀层晶粒细化,但稀土元素铈不与合金共沉积,只是起到改变镀层组织结构的作用.     

Ultrafine Dual‐Phased Carbide Nanocrystals Confined in Porous Nitrogen‐Doped Carbon Dodecahedrons for Efficient Hydrogen Evolution Reaction

Designing novel non‐noble electrocatalysts with controlled structures and composition remains a great challenge for efficient hydrogen evolution reaction (HER). Herein, a rational synthesis of ultrafine carbide nanocrystals confined in porous nitrogen‐doped carbon dodecahedrons (PNCDs) by annealing functional zeolitic imidazolate framework (ZIF‐8) with molybdate or tungstate is reported. By controlling the substitution amount of MO₄ units (M = Mo or W) in the ZIF‐8 framework, dual‐phase carbide nanocrystals confined in PNCDs (denoted as MC‐M₂C/PNCDs) can be obtained, which exhibit superior activity toward the HER to the single‐phased MC/PNCDs and M₂C/PNCDs. The evenly distributed ultrafine nanocrystals favor the exposure of active sites. PNCDs as the support facilitate charge transfer and protect the nanocrystals from aggregation during the HER process. Moreover, the strong coupling interactions between MC and M₂C provide beneficial sites for both water dissociation and hydrogen desorption. This work highlights a new feasible strategy to explore efficient electrocatalysts via engineering on nanostructure and composition.     

Porous Microrod Arrays Constructed by Carbon‐Confined NiCo@NiCoO2 Core@Shell Nanoparticles as Efficient Electrocatalysts for Oxygen Evolution

The study of cost‐efficient and high‐performance electrocatalysts for oxygen evolution reaction (OER) has attracted much attention. Here, porous microrod arrays constructed by carbon‐confined NiCo@NiCoO₂ core@shell nanoparticles (NiCo@NiCoO₂/C PMRAs) are fabricated by the reductive carbonization of bimetallic (Ni, Co) metal–organic framework microrod arrays (denoted as NiCo‐MOF MRAs) and subsequent controlled oxidative calcination. They successfully combine the desired merits including large specific surface areas, high conductivity, and multiple electrocatalytic active sites for OER. In addition, the oxygen vacancies in NiCo@NiCoO₂/C PMRAs significantly improve the conductivity of NiCoO₂ and accelerate the kinetics of OER. The above advantages obviously enhance the electrocatalytic performance of NiCo@NiCoO₂/C PMRAs. The experimental results demonstrate that the NiCo@NiCoO₂/C PMRAs as electrocatalysts exhibit high catalytic activity, low overpotential, and high stability for OER in alkaline media. The strategy reported will open up a new route for the fabrication of porous bimetallic composite electrocatalysts derived from MOFs with controllable morphology for electrochemical energy conversion devices.     

Borocarbonitrides as Metal‐Free Catalysts for the Hydrogen Evolution Reaction

Hydrogen generation by water splitting is clearly a predominant and essential strategy to tackle the problems related to renewable energy. In this context, the discovery of proper catalysts for electrochemical and photochemical water splitting assumes great importance. There is also a serious intent to eliminate platinum and other noble metal catalysts. To replace Pt by a non‐metallic catalyst with desirable characteristics is a challenge. Borocarbonitrides, (B_xC_yN_z) which constitutes a new class of 2D material, offer great promise as non‐metallic catalysts because of the easy tunability of bandgap, surface area, and other electronic properties with variation in composition. Recently, B_xC_yN_z composites with excellent electrochemical and photochemical hydrogen generation activities have been found, especially noteworthy being the observation that B_xC_yN_z with a carbon‐rich composition or its nanocomposites with MoS₂ come close to Pt in electrocatalytic properties, showing equally good photochemical activity.     

Dislocation-Strained IrNi Alloy Nanoparticles Driven by Thermal Shock for the Hydrogen Evolution Reaction

Designing high-performance and low-cost electrocatalysts is crucial for the electrochemical production of hydrogen. Dislocation-strained IrNi nanoparticles loaded on a carbon nanotube sponge (DSIrNi@CNTS) driven by unsteady thermal shock in an extreme environment are reported here as a highly efficient hydrogen evolution reaction (HER) catalyst. Experimental results demonstrate that numerous dislocations are kinetically trapped in self-assembled IrNi nanoparticles due to the ultrafast quenching and different atomic radii, which can induce strain effects into the IrNi nanoparticles. Such strain-induced high-energy surface structures arising from bulk defects (dislocations), are more likely to be resistant to surface restructuring during catalysis. The catalyst exhibits outstanding HER activity with only 17 mV overpotential to achieve 10 mA cm⁻² in an alkaline electrolyte with fabulous stability, exceeding state-of-the-art Pt/C catalysts. These density functional theory results demonstrate that the electronic structure of as-synthesized IrNi nanostructure can be optimized by the strain effects induced by the dislocations, and the free energy of HER can be tuned toward the optimal region.     

Toward Activity Origin of Electrocatalytic Hydrogen Evolution Reaction on Carbon‐Rich Crystalline Coordination Polymers

The fundamental understanding of electrocatalytic active sites for hydrogen evolution reaction (HER) is significantly important for the development of metal complex involved carbon electrocatalysts with low kinetic barrier. Here, the MS_x N_y (M = Fe, Co, and Ni, x /y are 2/2, 0/4, and 4/0, respectively) active centers are immobilized into ladder‐type, highly crystalline coordination polymers as model carbon‐rich electrocatalysts for H₂ generation in acid solution. The electrocatalytic HER tests reveal that the coordination of metal, sulfur, and nitrogen synergistically facilitates the hydrogen ad‐/desorption on MS_x N_y catalysts, leading to enhanced HER kinetics. Toward the activity origin of MS₂N₂, the experimental and theoretical results disclose that the metal atoms are preferentially protonated and then the production of H₂ is favored on the M? N active sites after a heterocoupling step involving a N‐bound proton and a metal‐bound hydride. Moreover, the tuning of the metal centers in MS₂N₂ leads to the HER performance in the order of FeS₂N₂ > CoS₂N₂ > NiS₂N₂. Thus, the understanding of the catalytic active sites provides strategies for the enhancement of the electrocatalytic activity by tailoring the ligands and metal centers to the desired function.     

Big to Small: Ultrafine Mo2C Particles Derived from Giant Polyoxomolybdate Clusters for Hydrogen Evolution Reaction

Due to its electronic structure, similar to platinum, molybdenum carbides (Mo₂C) hold great promise as a cost‐effective catalyst platform. However, the realization of high‐performance Mo₂C catalysts is still limited because controlling their particle size and catalytic activity is challenging with current synthesis methods. Here, the synthesis of ultrafine β‐Mo₂C nanoparticles with narrow size distribution (2.5 ± 0.7 nm) and high mass loading (up to 27.5 wt%) on graphene substrate using a giant Mo‐based polyoxomolybdate cluster, Mo₁₃₂ ((NH₄)₄₂[Mo₁₃₂O₃₇₂(CH₃COO)₃₀(H₂O)₇₂]·10CH₃COONH₄·300H₂O) is demonstrated. Moreover, a nitrogen‐containing polymeric binder (polyethyleneimine) is used to create Mo? N bonds between Mo₂C nanoparticles and nitrogen‐doped graphene layers, which significantly enhance the catalytic activity of Mo₂C for the hydrogen evolution reaction, as is revealed by X‐ray photoelectron spectroscopy and density functional theory calculations. The optimal Mo₂C catalyst shows a large exchange current density of 1.19 mA cm^?2, a high turnover frequency of 0.70 s^?1 as well as excellent durability. The demonstrated new strategy opens up the possibility of developing practical platinum substitutes based on Mo₂C for various catalytic applications.     

Crystalline Ru0.33Se Nanoparticles‐Decorated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction

Nowadays, the state‐of‐the‐art electrocatalysts for hydrogen evolution reaction (HER) are platinum group metals. Nonetheless, Pt‐based catalysts show decreased HER activity in alkaline media compared with that in acidic media due to the sluggish dissociation process of H₂O on the surface of Pt. With a cost 1/25 that of Pt, Ru demonstrates a favorable dissociation kinetics of absorbed H₂O. Herein, crystalline Ru_0.33Se nanoparticles are decorated onto TiO₂ nanotube arrays (TNAs) to fabricate Ru_0.33Se @ TNA hybrid for HER. Owing to the large‐specific surface area, Ru_0.33Se nanoparticles are freely distributed and the particle aggregation is eliminated, providing more active sites. The contracted electron transport pathway rendered by TiO₂ nanotubes and the synergistic effect at the interface significantly improve the charge transfer efficiency in the hybrid catalyst. Compared with Ru_0.33Se nanoparticles deposited directly on the Ti foil (Ru_0.33Se/Ti) or carbon cloth (Ru_0.33Se/CC), Ru_0.33Se @ TNA shows an enhanced catalytic activity with an overpotential of 57 mV to afford a current density of 10 mA cm^?2, a Tafel slope of 50.0 mV dec^?1. Furthermore, the hybrid catalyst also exhibits an outstanding catalytic stability. The strategy here opens up a new synthetic avenue to the design of highly efficient hybrid electrocatalysts for hydrogen production.