Nitrogen-doped graphene microtubes with opened inner voids: Highly efficient metal-free electrocatalysts for alkaline hydrogen evolution reaction

A facile method was developed to fabricate nitrogen-doped graphene microtubes (N-GMT) with ultra-thin walls of 1–4 nm and large inner voids of 1–2 μm. The successful introduction of nitrogen dopants afforded N-GMT more active sites for significantly enhanced hydrogen evolution reaction (HER) activity, achieving a current density of 10 mA·cm^–2 at overpotentials of 0.464 and 0.426 V vs. RHE in 0.1 and 6 M KOH solution, respectively. This HER performance surpassed that of the best metal-free catalyst reported in basic solution, further illustrating the great potential of N-GMT as an efficient HER catalyst for real applications in water splitting and chlor-alkali processes.

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Hierarchical Ni3S4@MoS2 nanocomposites as efficient electrocatalysts for hydrogen evolution reaction

Hydrogen evolution reaction (HER) through water splitting is a promising way to solve the energy short-age.Noble-metal-free HER electrocatalysts with high efficiency is very important for practical applica-tions.Herein,we prepare the Ni3S4@MoS2 electrocatalyst on carbon cloth (CC) through a two-step hy-drothermal process.The Ni3S4 nanorods are uniformly integrated with the MoS2 nanosheets,forming a hierarchical structure and heterogeneous interfaces.The fast electron transfer on the interface en-hances the kinetics of catalytic reaction.The hierarchical structure provides more exposed active sites.The Ni3S4@MoS2/CC exhibits good catalytic activity and long-term stability for HER.This work provided a practicable strategy to develop efficient electrocatalysts for HER in alkaline media.     

Fundamental aspects and recent advances in transition metal nitrides as electrocatalysts for hydrogen evolution reaction: A review

With increasing human population, sustainable energy production has become one of the most persistent and significant problems of the current century. Hydrogen is considered to be the best clean fuel for future energy requirements. As a substitute of fossil fuels, hydrogen is readily provided by an electrocatalytic hydrogen evolution reaction that splits water molecules. Conventional electrocatalysts based on noble metals are scarce and considerably expensive for large-scale hydrogen production, necessitating the search for low-cost earth abundant alternatives. In this context, transition metal nitrides have gained considerable attention as competent electrocatalytic materials for water splitting. This review presents recent advancements and progress on transition metal nitrides as efficient and cost-effective electrocatalysts for hydrogen production. After overviewing the fundamental aspects of the hydrogen evolution reaction (HER), the review discusses various synthetic strategies for developing transition metal nitrides. Discussed herein are titanium nitrides, vanadium nitrides, iron nitrides, nickel nitrides, molybdenum nitrides, tungsten nitrides, and their composite electrocatalysts employed in HER applications. Some design viewpoints for improving the electrocatalytic activity are systematically proposed. Finally, the review discusses challenges and future perspectives for the advancement of non-noble metal-based electrocatalysts.     

MoS_(2)/Ru异质结构的制备及其电催化析氢反应性能EI北大核心CSCD

二维层状二硫化钼(MoS_(2))是一种非常有前景的替代贵金属铂的电水解制氢催化剂。然而,MoS_(2)电子导电性较差,且在碱性氢析出反应(HER)中对水分子吸附/裂解的活化能垒较高,限制其在碱性电水解的应用。通过一步水热法将MoS_(2)纳米片均匀生长在三维导电碳布(CC)上,以有效提高电极导电性。随后在RuCl_(3)的乙醇溶液中通过溶剂热法可控制备超小Ru纳米颗粒负载MoS_(2)纳米片,形成CC@MoS_(2)/Ru异质结构。Ru的负载能有效促进水吸附/裂解反应,从而和MoS_(2)协同催化HER。采用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等方法对MoS_(2)/Ru进行结构和形貌表征。结果表明:MoS_(2)呈纳米片状交错生长在碳布上,并且超小Ru纳米颗粒(平均粒径2.5 nm)均匀负载在MoS_(2)纳米片上。将CC@MoS_(2)/Ru作为工作电极,石墨棒和Hg/HgO电极分别为对电极和参比电极进行碱性HER测试。在电流密度为-10 mA·cm^(-2)下的过电位仅为71.3 mV,Tafel斜率为104.8 mV·dec^(-1)。通过对其进行计时电位滴定法稳定性测试,发现在恒电流密度-10 mA·cm^(-2)下能够维持至少35 h而没有明显性能衰减。     

电沉积非晶Ni-Fe-P涂层析氢催化性能研究

采用直流电镀技术,通过改变电沉积电流密度制备了不同的非晶Ni-Fe-P涂层。采用稳态极化技术比较不同电流密度下电镀Ni-Fe-P合金涂层电化学催化析氢活性,发现电流密度200A/m2电沉积的Ni-Fe-P合金涂层的电化学催化析氢性能最好。通过XRD分析镀层相结构,SEM观察涂层表面的微观结构及EDX分析表面成分,研究影响非晶Ni-Fe-P合金涂层的析氢电催化活性原因。结果表明,影响非晶Ni-Fe-P合金涂层电催化活性的主要因素是镀层中Fe、P元素含量。当Fe的含量最大18.63%(原子分数),P的含量最小13.14%(原子分数)时,非晶Ni-Fe-P涂层电催化析氢活性最好。2     

Electrodeposited Ni-S intermetallic compound film electrodes for hydrogen evolution reaction in alkaline solutions

Tailoring of nickel-sulfur (Ni-S) intermetallic compound film electrodes for hydrogen evolution reaction in alkaline solutions was attempted by electrodeposition from a typical Watts bath containing sodium thiosulfate as sulfur source and sulfosalicylic acid as additive. The XRD analysis shows that the as-deposited Ni-S film electrode with fine morphological features comprised of intermetallic compound phase structure and amorphous phase structure. The intermetallic compound film electrodes generate a higher catalytic activity for the hydrogen evolution reaction in alkaline solution in comparison with Ni-S film electrodes comprised of amorphous phase structures, even with commercial Ni mesh or Ni/RuO₂ composite electrode.     

氮掺杂碳纳米纤维包覆超细碳化钼/氮化钼异质结构用于碱性条件下电催化析氢

高效非贵金属催化剂对于推进析氢反应(HER)的大规模工业化至关重要.碳化钼(Mo₂C)因其类似铂的能带密度和优良的中间产物吸附特性,有望替代贵金属基材料成为具有前景的催化剂.然而,它在常规制备过程中存在严重的晶体过度生长和团聚问题,导致催化效率低.本研究利用三聚氰胺辅助法制备了含有丰富表面和界面的超细碳化钼/氮化钼(Mo₂C/Mo₂N)异质结构,并同时将其嵌入到氮掺杂碳纳米纤维(CNFs)中.Mo₂C/Mo₂N异质结构的协同作用与超细纳米晶表面暴露的丰富活性位点共同提高了电催化活性,而氮掺杂碳纳米纤维框架保证了快速的电荷转移和良好的结构稳定性.此外,原位形成的Mo₂C/Mo₂N晶体与碳基质之间存在较强的界面耦合作用,进一步提高了电子电导率和电催化活性.得益于这些优势,Mo₂C/Mo₂N@N-CNFs在碱性溶液中表现出优异的电催化析氢性能,在电流密度10 mV cm^-2时具有75 mV的低过电势,优于单相Mo₂C@N-CNFs对比样以及近期报道的Mo₂C/Mo₂N基催化剂.这个合成方法集成了异质结构、纳米化和碳修饰策略,为设计高效率电催化材料提供了新的参考.     

基于简易微波方法制备高性能MoS2/石墨烯纳米复合材料用于高效析氢反应（英文）

用于析氢反应(HER)的低成本、高效能催化剂对于推进基于清洁氢气的能源工业非常重要.二维二硫化钼(MoS2)具有显著的催化性能,因而已被人们广泛深入研究.然而,大多数现有的合成方法耗时、复杂且效率较低.本文通过超快(60秒)微波引发的方法生产MoS2/石墨烯催化剂.石墨烯的高比表面积和导电性为MoS2纳米片的生长提供了有利的导电网络和快速电荷转移动力.文中制备的MoS2/石墨烯纳米复合材料在酸性介质中对HER表现出优异的电催化活性,具有62 mV的低起始电位,高阴极电流和43.3mV/dec的Tafel斜率.除了优异的催化活性外, MoS2/石墨烯还具有较长的循环稳定性,在250 mV的过电位下阴极电流密度高达1000 mA cm^-2.此外, MoS2/石墨烯催化剂在30–120°C范围内具有出色的HER活性和36.51 kJ mol^-1的低活化能,提供了潜在的大批量生产和制备的机会.     

Strategies for design of electrocatalysts for hydrogen evolution under alkaline conditions

Electrocatalytic hydrogen evolution reaction (HER) in alkaline environments is one of the major energy conversion processes in water electrolysis technology. Very active and cost-effective catalysts are highly desirable for alkaline HER not only for its industrial value but also for its fundamental importance in studying all electrocatalytic reactions occurring on cathode electrodes. However, to date, the reaction mechanism of alkaline HER is still under debate, which makes the design of catalysts largely a trial-and-error process. To address this issue, here we present strategies for the design of alkaline HER catalysts based on the current knowledge of the reaction mechanism by emphasizing the connection between the atomic-level materials engineering and reaction fundamentals. Particularly, we focus on the improvement of the inherent electronic structure of the materials to achieve desired interactions between the catalysts and reactive intermediates. By showing several successful examples of both theoretical and experimental design strategies, we aim to provide direct guidelines toward the design of catalysts for HER under alkaline conditions.     

Millisecond-timescale electrodeposition of platinum atom-doped molybdenum oxide as an efficient electrocatalyst for hydrogen evolution reaction

We present a straightforward method for one-pot electrodeposition of platinum atoms-doped molybdenum oxide (Pt·MoO_3−x) films and show their superior electrocatalytic activity in the hydrogen evolution reaction (HER). A ~15-nm-thick Pt·MoO_3−x film was prepared by one-pot electrodeposition at −0.8 V for 1 ms. Due to considerably different solute concentrations, the content of Pt atoms in the electrodeposited composite electrocatalyst is low. No Pt crystals or islands were observed on the flat Pt·MoO_3−x films, indicating that Pt atoms were homogeneously dispersed within the MoO_3−x thin film. The catalytic performance and physicochemical features of Pt·MoO_3−x as a HER electrocatalyst were characterized. The results showed that our Pt·MoO_3−x film exhibits 23- and 11-times higher current density than Pt and MoO_3−x electrodeposited individually under the same conditions, respectively. It was found that the dramatic enhancement in the HER performance was principally due to the abundant oxygen defects. The use of the developed one-pot electrodeposition and doping method can potentially be extended to various catalytically active metal oxides or hydroxides for enhanced performance in various energy storage and conversion applications.     

Wet-chemistry synthesis of cobalt carbide nanoparticles as highly active and stable electrocatalyst for hydrogen evolution reaction

Transition metal carbide (TMC) nanomaterials are promising alternatives to Pt,and are widely used as heterogeneous electrocatalysts for the electrochemical hydrogen evolution reaction (HER).In this work,a bromide-induced wet-chemistry strategy to synthesize Co2C nanopartides (NPs) was developed.Such NPs exhibited high electrocatalytic activity (η =181 mV for j =-10 mA.cm-2) and long-term stability (no obvious performance decrease after 4,000 cycles) for the HER.This study will pave the way for the design and fabrication of TMC NPs via a wetchemistry method,and will have significant impacts on broader areas such as nanocatalysis and energy conversion.     

Boron nitride-based electrocatalysts for HER,OER, and ORR: A mini-review

A reliable and efficient solution to the current energy crisis and its associated environmental issues is provided by fuel cells, metal–air batteries and overall water splitting. The heart reactions for these technologies are oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Different supporters such as graphene, carbon nanotube, and graphitic carbon nitride have been used to avoid agglomeration of active materials and provide maximum active surface for these reactions. Among all the supporters, boron nitride (BN) gains extensive research attention due to its analogue with graphene and excellent stability with good oxidation and chemical inertness. In this mini-review, the well-known strategies (exfoliation, annealing, and CVD) used in the synthesis of BN with different morphologies for HER, OER and ORR applications have been briefly debated and summarized. The comparative analysis determines that the performance and stability of state-of-the-art electrocatalysts can be further boosted if they are deposited on BN. It is revealed that BN-based catalysts for HER, OER and ORR are rarely studied yet especially with non-noble transition metals, and this research direction should be studied deeply in future for practical applications.     

Defect-rich MoS<Subscript>2</Subscript> nanowall catalyst for efficient hydrogen evolution reaction

Designing efficient electrocatalysts for the hydrogen evolution reaction (HER) has attracted substantial attention owing to the urgent demand for clean energy to face the energy crisis and subsequent environmental issues in the near future.Among the large variety of HER catalysts,molybdenum disulfide (MoS2) has been regarded as the most famous catalyst owing to its abundance,low price,high efficiency,and definite catalytic mechanism.In this study,defect-engineered MoS2 nanowall (NW) catalysts with controllable thickness were fabricated and exhibited a significantly enhanced HER performance.Benefiting from the highly exposed active edge sites and the rough surface accompanied by the robust NW structure,the defect-rich MoS2 NW catalyst with an optimized thickness showed an ultralow onset overpotential of 85 mV,a high current density of 310.6 mA·cm-2 at η =300 mV,and a low potential of 95 mV to drive a 10 mA.cm-2 cathodic current.Additionally,excellent electrochemical stability was realized,making this freestanding NW catalyst a promising candidate for practical water splitting and hydrogen production.     

In-situ constructed Ru-rich porous framework on NiFe-based ribbon for enhanced oxygen evolution reaction in alkaline solution

Exploiting economical and high-efficient electrocatalysts of oxygen evolution reaction(OER)remains urgent in the field of sustainable hydrogen generation by water electrolysis.Ru-and Ir-based materials are benchmark electrocatalysts towards the OER,yet the precious metals are expensive and scarce.Herein,we develop a kind of Ru-doped NiFe-based catalyst with three-dimensional nanoporous surface(NP-Rux),which fulfils both performance and cost requirements for the OER electrocatalysis.This novel material can directly work as a support-free electrode and exhibits excellent OER performance with an ultralow overpotential of 245 mV at 10 mA cmr-2 and a small Tafel slope of 15 mV dec-1 as well as low charge transfer resistance.The superior performance could be rationalized as follows:(1)Generated Ru-rich nanoporous architecture can not only supply a large number of active sites but also facilitate mass transfer at the electrode/electrolyte interface;(2)Multiple metals(hydro)oxides generated on the surface have the synergistic catalytic effect for the OER;(3)The in-situ generation of(hydro)oxides and the firm bonding of nanoporous layer and the substrate allow for easy electron transfer.These features make NP-Rux a promising oxygen-evolving electrode material toward water electrolysis.     

共掺杂三维石墨烯的制备及其电催化析氢性能的研究

选择天然石墨鳞片为原料,采用改进的Hummers法制备出氧化石墨(GO),再以硫脲、硫酸亚铁和氯化镍为改性剂,利用化学还原法和自组装法制备了氮、硫、铁、镍共掺杂三维石墨烯电极材料。通过扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线能谱(EDS)等测试手段对材料进行分析表征,研究了不同因素对其析氢反应活性(HER)的影响,并通过均匀试验设计确定了制备的最佳工艺条件。结果表明:所制备的电极材料具有丰富的孔结构和完整的三维结构,石墨烯片层间距为0.3734 nm,并且无明显垛叠团聚,在酸性条件下显示出较高的HER活性,在电流密度为10 mA/cm2时,析氢过电位为-158 mV,塔菲尔(Tafel)斜率为74.33 mV/dec。     

碱液中镍电极的析氢机理

研究镍电极在碱液中的析氢机理对开发二次清洁能源有指导意义,过去对其研究不够.通过Tafel曲线和电化学阻抗谱对镍电极在KOH溶液中的析氢机理进行了研究.结果表明,过电位低于600 mV时,析氢服从复合脱附机理,反应历程为电化学步骤+复合脱附步骤;过电位高于600 mV时,析氢服从迟缓放电机理或电化学脱附机理,反应历程为电化学步骤+电化学脱附步骤.     

Plasma tailoring in WTe2 nanosheets for efficiently boosting hydrogen evolution reaction

2D transition metal dichalcogenides(TMDs)have been considered as promising non-precious electro-catalysts for the hydrogen evolution reaction(HER).However,their limited active sites and poor electric conductivity pose a significant hurdle to their HER performance,resulting in a large overpotential.Here,we report the defect engineering in ultrathin tungsten telluride(WTe2)nanosheets with semimetal nature to improve hydrogen evolution effectively.We find that the oxygen plasma etching imposes a cutting effect on WTe2 nanosheets,resulting in a large number of tungsten vacancies.Particularly,the sample after plasma treatment for 10 min shows a feather-like structure with an overpotential of 251 mV at 10 mA/cm2 and a Tafel slope of 94 mV/dec,which is 4 times lower than the Tafel slope of pris-tine nanosheets.Further first-principles calculations shed light on the evolution of defect-rich WTe2 nanosheets and offer rational explanation to their superiority in efficient hydrogen evolution.     

Surface dissolution and amorphization of electrocatalysts during oxygen evolution reaction: Atomistic features and viewpoints

Electrochemical electrolysis with an aqueous electrolyte is a key method to obtain green hydrogen energy, convert carbon dioxide into high value-added carbon-based chemicals, and produce ammonia by nitrogen reduction at ambient conditions. For better efficiency of these electrolysis processes, lowering the comparatively large activation barrier of the sluggish oxygen evolution reaction (OER) at the anode side is necessary. Therefore, suitable electrocatalysts should be adopted to facilitate the OER. As a highly oxidizing environment along with high overpotential is unavoidable at the anode during electrolysis, degradation of both the activity and durability of OER catalysts inevitably takes place. In this Review, we classify four significant origins directly affecting the stability of oxide-based OER catalysts: (1) Alkali and alkaline-earth metal dissolution; (2) transition-metal leaching; (3) lattice oxygen evolution; and (4) rapid dissolution of phosphorus and chalcogens. In particular, because these origins usually induce amorphization or reconstruction at the surface, we systematically summarize atomic-level evidence largely based on transmission electron microscopy in each section. Providing integrated viewpoints for a better understanding of catalyst degradation, we believe that this Review offers valuable insight toward designing new OER catalysts with enhanced durability and activity.     

1.82 wt.% Pt/N,P co-doped carbon overwhelms 20 wt.% Pt/C as a high-efficiency electrocatalyst for hydrogen evolution reaction

Cost-effective electrocatalysts for the hydrogen evolution reaction (HER) play a key role in the field of renewable energy. Although tremendous efforts have been devoted to the search of alternative materials, Pt/C is still the most efficient electrocatalyst for the HER. Nevertheless, decreasing the loading of Pt in the designed eletrocatalysts is of significance. However, with low Pt loading, it is challenging to maintain excellent catalytic performance. Herein, a new catalyst (Pt/NPC) was prepared by dispersing Pt nanoparticles (PtNPs) with an average diameter of 1.8 nm over a three-dimensional (3D) carbon network co-doped with N and P. Because of the high electronegativity of the N and P dopants, PtNPs were uniformly dispersed on the carbon network via high electronic affinity between Pt and carbon, affording a Pt/NPC catalyst; Pt/NPC exhibited superior HER activity, attributed to the down-shift of the Pt d-band caused by the donation of charge from N and P to Pt. The results show that Pt/NPC with an ultralow Pt loading of 1.82 wt.% exhibits excellent HER performance, which corresponds to a HER mass activity 20.6-fold greater than that observed for commercial 20% Pt/C at an overpotential of 20 mV vs. RHE.

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