纳米晶碳化钨薄膜的析氢催化性能

采用等离子体增强化学气相沉积法制备了具有纳米结构的碳化钨薄膜, 采用XRD、EDS、SEM方法表征了薄膜的表面形貌、化学组成和物相结构. 这种碳化钨纳米晶薄膜具有巨大的电化学比表面积、很好的电催化活性和电化学稳定性. 通过测试和计算表明, 几何面积为1cm²碳化钨薄膜/泡沫镍电极、碳化钨薄膜/镍电极的电化学比表面积分别为83.21和64.13cm2; 该薄膜电极材料的a值为0.422～0.452V, 接近低超电势材料; 析氢交换电流密度为4.02～4.22×10^-4A/cm²; 当超电势为263mV时, 其析氢反应的活化能为45.62～45.77kJ/mol.     

Self-Supported Transition-Metal-Based Electrocatalysts for Hydrogen and Oxygen Evolution

Electrochemical water splitting is a promising technology for sustainable conversion, storage, and transport of hydrogen energy. Searching for earth-abundant hydrogen/oxygen evolution reaction (HER/OER) electrocatalysts with high activity and durability to replace noble-metal-based catalysts plays paramount importance in the scalable application of water electrolysis. A freestanding electrode architecture is highly attractive as compared to the conventional coated powdery form because of enhanced kinetics and stability. Herein, recent progress in developing transition-metal-based HER/OER electrocatalytic materials is reviewed with selected examples of chalcogenides, phosphides, carbides, nitrides, alloys, phosphates, oxides, hydroxides, and oxyhydroxides. Focusing on self-supported electrodes, the latest advances in their structural design, controllable synthesis, mechanistic understanding, and strategies for performance enhancement are presented. Remaining challenges and future perspectives for the further development of self-supported electrocatalysts are also discussed.     

多孔Ni-WC复合电极的制备及其在酸性溶液中的电催化析氢性能

目前,关于多孔Ni-WC电极的电催化析氢(HER)性能的报道较少。以多孔海绵镍为基体,采用复合电沉积制备多孔Ni-(WC)x复合电极。运用扫描电镜(SEM)和X射仪线衍射仪(XRD)表征电极的表面形貌和微观结构,通过阴极极化、电化学阻抗(EIS)、循环伏安、计时电流法研究多孔Ni-(WC)x电极在0.5 mol/L H2SO4溶液中的电催化析氢性能。结果表明:与多孔基体Ni电极相比,多孔Ni-(WC)x电极具有较低的析氢过电位、较低的电化学反应阻抗、较小的表观活化能以及较大的交换电流密度;随着镀液中WC浓度的升高,所制备的多孔Ni-(WC)x电极的电催化析氢活性增强,其中Ni-(WC)40电极的表观交换电流密度是多孔Ni基体电极的966.7倍,其表观活化能为5.95 kJ/mol,并具有较好的耐蚀性和析氢稳定性。     

Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte

Nitrogen and sulfur‐codoped graphene composites with Co₉S₈ (NS/rGO‐Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO₂ catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only ?0.193 V to reach 10 mA cm^?2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half‐wave potential in ORR and the potential to reach 10 mA cm^?2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm^?2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S‐codoped rGO, and Co₉S₈ nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions.     

Construction of Nitrogen-Doped Biphasic Transition-Metal Sulfide Nanosheet Electrode for Energy-Efficient Hydrogen Production via Urea Electrolysis

Urea-assisted hybrid water splitting is a promising technology for hydrogen (H₂) production, but the lack of cost-effective electrocatalysts hinders its extensive application. Herein, it is reported that Nitrogen-doped Co₉S₈/Ni₃S₂ hybrid nanosheet arrays on nickel foam (N-Co₉S₈/Ni₃S₂/NF) can act as an active and robust bifunctional catalyst for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER), which could drive an ultrahigh current density of 400 mA cm⁻² at a low working potential of 1.47 V versus RHE for UOR, and gives a low overpotential of 111 mV to reach 10 mA cm⁻² toward HER. Further, a hybrid water electrolysis cell utilizing the synthesized N-Co₉S₈/Ni₃S₂/NF electrode as both the cathode and anode displays a low cell voltage of 1.40 V to reach 10 mA cm⁻², which can be powered by an AA battery with a nominal voltage of 1.5 V. The density functional theory (DFT) calculations decipher that N-doped heterointerfaces can synergistically optimize Gibbs free energy of hydrogen and urea, thus accelerating the catalytic kinetics of HER and UOR. This work significantly advances the development of the promising cobalt–nickel-based sulfide as a bifunctional electrocatalyst for energy-saving electrolytic H₂ production and urea-rich innocent wastewater treatment.     

化学镀Ni-Co-W-P及其析氢性能的研究

用化学镀方法制备出Ni-Co-W-P合金电极,测量了其在1 mol/L NaOH溶液中的阴极极化曲线并研究了其析氢电催化活性.试验表明,在相同的电流密度下,Ni-Co-P,Ni-W-P和Ni-Co-W-P合金电极的析氢过电位较Fe电极降低,其中Ni-Co-W-P的析氢过电位降低约230 mV,XRD试验显示其镀层为非晶态.并进一步测试了其在7 mol/L KOH中的连续电解曲线.结果表明:Ni-Co-W-P合金电极比Ni-Co-P,Ni-W-P合金电极具有更好的析氢电催化活性和电化学稳定性,有利于降低槽压,减少能耗.     

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.     

Confining Sub-Nanometer Pt Clusters in Hollow Mesoporous Carbon Spheres for Boosting Hydrogen Evolution Activity

Electrochemical water splitting is considered as a promising approach to produce clean and sustainable hydrogen fuel. As a new class of nanomaterials with high ratio of surface atoms and tunable composition and electronic structure, metal clusters are promising candidates as catalysts. Here, a new strategy is demonstrated to synthesize active and stable Pt-based electrocatalysts for hydrogen evolution by confining Pt clusters in hollow mesoporous carbon spheres (Pt₅/HMCS). Such a structure would effectively stabilize the Pt clusters during the ligand removal process, leading to remarkable electrocatalytic performance for hydrogen production in both acidic and alkaline solutions. Particularly, the optimal Pt₅/HMCS electrocatalyst exhibits 12 times the mass activity of Pt in commercial Pt/C catalyst with similar Pt loading. This study exemplifies a simple yet effective approach to improve the cost effectiveness of precious-metal-based catalysts with stabilized metal clusters.     

Interfacial Engineering of MoO2-FeP Heterojunction for Highly Efficient Hydrogen Evolution Coupled with Biomass Electrooxidation

Simultaneous highly efficient production of hydrogen and conversion of biomass into value-added products is meaningful but challenging. Herein, a porous nanospindle composed of carbon-encapsulated MoO₂-FeP heterojunction (MoO₂-FeP@C) is proposed as a robust bifunctional electrocatalyst for hydrogen evolution reaction (HER) and biomass electrooxidation reaction (BEOR). X-ray photoelectron spectroscopy analysis and theoretical calculations confirm the electron transfer from MoO₂ to FeP at the interfaces, where electron accumulation on FeP favors the optimization of H₂O and H* absorption energies for HER, whereas hole accumulation on MoO₂ is responsible for improving the BEOR activity. Thanks to its interfacial electronic structure, MoO₂-FeP@C exhibits excellent HER activity with an overpotential of 103 mV at 10 mA cm⁻² and a Tafel slope of 48 mV dec⁻¹. Meanwhile, when 5-hydroxymethylfurfural is chosen as the biomass for BEOR, the conversion is almost 100%, and 2,5-furandicarboxylic acid (FDCA) is obtained with the selectivity of 98.6%. The electrolyzer employing MoO₂-FeP@C for cathodic H₂ and anodic FDCA production requires only a low voltage of 1.486 V at 10 mA cm⁻² and can be powered by a solar cell (output voltage: 1.45 V). Additionally, other BEORs coupled with HER catalyzed by MoO₂-FeP@C also have excellent catalytic performance, implying their good versatility.     

氢气分离技术的研究现状

高纯氢气的制取已经成为21世纪材料领域的研究热点之一,而氢气分离技术作为制取高纯氢气的一个关键环节,尤为引人注目.介绍了氢气分离方法的原理、特点、应用和研究现状,探讨了氢气分离方法的现存问题及发展前景.     

膜分离法回收合成氨弛放气中氢气

介绍了膜分离的原理和应用。实践表明该方法具有效率高、流程简单、操作灵活容易、纯度高和收率高等优点。     

Combining Highly Dispersed Amorphous MoS3 with Pt Nanodendrites as Robust Electrocatalysts for Hydrogen Evolution Reaction

Surface modification of electrocatalysts to obtain new or improved electrocatalytic performance is currently the main strategy for designing advanced nanocatalysts. In this work, highly dispersed amorphous molybdenum trisulfide-anchored Platinum nanodendrites (denoted as Pt-a-MoS₃ NDs) are developed as efficient hydrogen evolution electrocatalysts. The formation mechanism of spontaneous in situ polymerization MoS₄²⁻ into a-MoS₃ on Pt surface is discussed in detail. It is verified that the highly dispersed a-MoS₃ enhances the electrocatalytic activity of Pt catalysts under both acidic and alkaline conditions. The potentials at the current density of 10 mA cm⁻² (η₁₀) in 0.5 m  sulfuric acid (H₂SO₄) and 1 m  potassium hydroxide (KOH) electrolyte are −11.5 and −16.3 mV, respectively, which is significantly lower than that of commercial Pt/C (−20.2 mV and −30.7 mV). This study demonstrates that such high activity benefits from the interface between highly dispersed a-MoS₃ and Pt sites, which act as the preferred adsorption sites for the efficient conversion of hydrion (H⁺) to hydrogen (H₂). Additionally, the anchoring of highly dispersed clusters to Pt substrate greatly enhances the corresponding electrocatalytic stability.     

微孔二氧化硅膜的制备、氢气分离以及水热稳定性研究

利用溶胶-凝胶法在Υ-Al₂O₃/α-Al₂O₃多孔支撑体上合成了微孔二氧化硅膜,并用IR、TG、FESEM、N₂吸附以及气体渗透等手段对二氧化硅膜进行了研究.结果表明,200℃时H₂的渗透率达到2.3×10^-7mol·m^-2·Pa^-1·s^-1,H₂/CO₂的分离系数为8.0,然而当二氧化硅膜长期暴露于潮湿环境时,由于水气与孔表面羟基相互作用引起二氧化硅膜孔结构的崩溃,最终导致H₂渗透率和H₂/CO₂分离系数剧烈下降.     

Prereduction of Metal Oxides via Carbon Plasma Treatment for Efficient and Stable Electrocatalytic Hydrogen Evolution

Prereduction of transition metal oxides is a feasible and efficient strategy to enhance their catalytic activity for hydrogen evolution. Unfortunately, the prereduction via the common H₂ annealing method is unstable for nanomaterials during the hydrogen evolution process. Here, using NiMoO₄ nanowire arrays as the example, it is demonstrated that carbon plasma (C‐plasma) treatment can greatly enhance both the catalytic activity and the long‐term stability of transition metal oxides for hydrogen evolution. The C‐plasma treatment has two functions at the same time: it induces partial surface reduction of the NiMoO₄ nanowire to form Ni₄Mo nanoclusters, and simultaneously deposits a thin graphitic carbon shell. As a result, the C‐plasma treated NiMoO₄ can maintain its array morphology, chemical composition, and catalytic activity during long‐term intermittent hydrogen evolution process. This work may pave a new way for simultaneous activation and stabilization of transition metal oxide‐based electrocatalysts.     

增强微孔二氧化硅氢气分离膜疏水性的研究现状

综述了提高微孔二氧化硅膜疏水性的方法以及微孔二氧化硅膜材料在氢气分离方面的应用.孔表面羟基是导致微孔二氧化硅膜亲水的主要原因,因此在溶胶-凝胶反应阶段用疏水基团来修饰溶胶,可以在最终材料的孔表面引入疏水基团,降低羟基浓度,从而提高其疏水性.修饰后的二氧化硅膜孔结构没有显著的变化,可以应用于氢气分离等领域.     

我国自主研制成功首套空气分离设备和氢气分离设备的历程

叙述了建国初期大连化学厂遵照原东北人民政府工业部化学工业管理局1951年下达的《对大连化学厂三年恢复建设的原则决定》第2项＂空分及氢分的设备全部自行设计试制＂布署,自1952年开始自主设计试制空气分离设备和氢气设备,并相继于1953年7月12日,我国首套处理空气量6800m3/h空气分离设备制成投产;1955年,我国首套处理原料气量8800m3/h氢气分离设备制成投产的光辉历程。