Unveiling the role of Zn dopants in NiFe phosphide nanosheet for oxygen evolution reaction

Transition metal phosphides have been recognized as promising electrocatalysts for oxygen evolution reaction(OER) due to their low cost and high activity. However, the insufficient exposed active region limited the OER performance. Recently, the introduction of sacrificial dopants has been considered an effective strategy to enlarge the surface area. Herein, the Zn dopants are introduced in NiFe phosphide(NiFeZnP) nanosheet, which work as the sacrificial dopants to generate more exposed active N...     

钴掺杂硫化锌催化剂的制备及其电催化析氢性能

以硝酸钴、硝酸锌为主要原料,分别采用L-半胱氨酸和硫脲为硫源制备钴掺杂硫化锌,借助XRD、SEM、TEM等对其形貌及结构进行表征,并通过析氢实验探讨不同硫化方式对钴掺杂硫化锌电催化性能的影响。结果表明,以L-半胱氨酸硫化法制备的钴掺杂硫化锌催化剂结晶度高且具有更好的电催化析氢效果。     

纳米多孔Co的磷化物制备及其电催化析氢性能

采用脱合金化、水热合成和化学气相沉积制备纳米多孔Co、NiCo(OH)₂/Co和NiCo(OH)₂-P复合电极.通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)等方法表征电极材料的物相和形貌结构.在1 mol·L^-1的KOH溶液中,运用线性扫描伏安曲线(LSV)、交流阻抗谱(EIS)、循环伏安曲线(CV)等测试电极的电催化析氢性能.结果表明：纳米多孔Co、NiCo(OH)₂/Co、NiCo(OH)₂-P电极材料的析氢性能依次增加,化学气相沉积(CVD)磷化后的纳米多孔NiCo(OH)₂-P在10 mA·cm^-2电流密度下,其过电位为139 mV,Tafel斜率为123.57 mV·dec^-1,双电层电容为30.16 mF·cm^-2.经过1 000圈循环伏安耐久性实验后,纳米多孔NiCo(OH)₂-P电极在10 mA·cm^-2电流密度下,析氢过电...     

Transition-metal-doped Fe2O3 nanoparticles for oxygen evolution reaction

Hematite(α-Fe_2O_3)has been extensively studied as a promising photocatalyst,with the capacity to split water under visible light.To tune its electronic structure and improve the performance for oxygen evolution reaction(OER),high-quality single crystals ofα-Fe_2O_3nanoparticles were synthesized and doped by various transition metals(M=V,Cr,Mn,Zn,Co,Ni,Cu,Nb,Mo,Ti)by a molten-salt flux method.Optical,electronic and catalytic properties of transition-metal-dopedα-Fe_2O_3(TM-dopedα-Fe_2O_3)have been systematically investigated.Cobalt has been identified as the best dopant forα-Fe_2O_3,reducing the OER overpotential by 0.16 V with respect to the undoped.     

Multicomponent transition metal phosphide for oxygen evolution

Transition metal phosphides(TMPs)have exhibited decent performance in an oxygen evolution reaction(OER),which is a kinetic bottleneck in many energy storages and conversion systems.Most reported catalysts are composed of three or fewer metallic components.The inherent complexity of multicomponent TMPs with more than four metallic components hinders their investigation in rationally designing the structure and,more importantly,comprehending the component-activity correlation.Through hydrothermal growth and subsequent phosphor-ization,we reported a facile strategy for combining TMPs with tunable elemental compositions(Ni,Fe,Mn,Co,Cu)on a two-dimensional ti-tanium carbide(MXene)flake.The obtained TMPs/MXene hybrid nanostructures demonstrate homogeneously distributed elements.They ex-hibit high electrical conductivity and strong interfacial interaction,resulting in an accelerated reaction kinetics and long-term stability.The res-ults of different component catalysts’OER performance show that NiFeMnCoP/MXene is the most active catalyst,with a low overpotential of 240 mV at 10 mA·cm?2,a small Tafel slope of 41.43 mV·dec?1,and a robust long-term electrochemical stability.According to the electrocata-lytic mechanism investigation,the enhanced NiFeMnCoP/MXene OER performance is due to the strong synergistic effect of the multi-ele-mental composition.Our work,therefore,provides a scalable synthesis route for multi-elemental TMPs and a valuable guideline for efficient MXene-supported catalysts design.     

Effect of supporting materials on the electrocatalytic activity,stability and selectivity of noble metal-based catalysts for oxygen reduction and hydrogen evolution reactions

Carbonaceous and alternative supporting materials for platinum(Pt) and palladium(Pd) have been explored for the cathodic electrocatalysis in low-temperature fuel cells. Pd and Pt are widely used for catalysis owing to their remarkable electrocatalytic activity toward water splitting and fuel cell reactions. Supporting materials play a paramount role in defining electrocatalytic properties such as durability, selectivity, and activity. The conventional supporting material such as carbon black is unable to fit all the requirements under the severe operating conditions of fuel cells due to its poor corrosion resistance and limited mass transport of fuels to active catalyst sites. Nowadays the scientific research is being concentrated on devising different altered carbonic and carbonfree supporting materials for catalysts to improve the catalytic activity, stability, and selectivity of noble metal electrocatalysts. Lately, Pt, Pd and their alloy catalysts supported on modified carbonaceous and carbon-free materials have attracted solid interest owing to their prominent characteristics contributing to the remarkable fuel cell efficacy. Therefore, it is reasonable to explore this theme, regarding a variety of supporting materials,their advantages, drawbacks and future perspectives. In this mini-review, we selectively summarize recent advancements on several types of key supporting materials: carbon(graphene, carbon nanotubes, mesoporous carbon, and doped carbon nanostructures), non-carbon(transition metals oxides, borides, nitrides, and carbides)and hybrid nanocomposites.     

Magnetic field induced synthesis of (Ni,Zn)Fe2O4 spinel nanorod for enhanced alkaline hydrogen evolution reaction

Recently, the introduction of external fields(light, thermal, magnetism, etc.) during electrocatalysis reactions gradually becomes a new strategy to modulate the catalytic activities. In this work, an external magnetic field was innovatively employed for the synthesis progress of(Ni, Zn)Fe₂O₄spinel oxide(M-(Ni, Zn)Fe₂O₄). Results indicated the magnetic field(≤250 m T) would affect the morphology of catalyst due to the existing Fe ions, inducing the M-(...     

纳米多孔Ni的制备及其电催化析氢性能研究

采用快速凝固结合脱合金的方法制备纳米多孔Ni,通过扫描电子显微镜(SEM)、X射线衍射仪(XRD)对试样进行物相分析和形貌表征,并使用线性扫描伏安(LSV)、循环伏安(CV)、交流阻抗(EIS)等方法测试纳米多孔Ni电极的电催化析氢性能.结果表明:Ni₅Al₉₅前驱体合金在65 ℃条件下经4 h脱合金化后获得多层次、双连续的纳米多孔Ni.在50 mA·cm^－2电流密度下,25 ℃时析氢过电位为257 mV,双电层电容为4.7 mF·cm^－2,在析氢反应过程中表观活化能为26.06 kJ·mol^－1,电化学脱附是整个反应的控制步骤.经过1 000圈循环伏安耐久实验后,纳米多孔Ni电极在25 ℃下极化曲线基本保持原状,50 mA·cm^－2电流密度下析氢过电位减小6 mV,表现出优良的析氢稳定性.     

脉冲电沉积制备非晶态Ni-Mo合金及析氢性能

电解水产氢具有原材料来源丰富、生产过程清洁、效率较高的优势,已经成为广泛研究的技术之一.通过脉冲电沉积技术,在不同的电流密度和占空比下,制备了不同的非晶态Ni-Mo合金镀层,研究了电流密度和占空比对镀层性能的影响.结果表明:随着占空比和电流密度的增大Mo含量减小,表面更加粗糙,在电流密度为2.5 A·dm^－2和占空比0.8下,可获得表面极为粗糙的非晶态Ni-Mo合金镀层,另外,占空比为0.6和电流密度为2.0 A·dm^－2下获得晶粒尺寸较小的合金镀层.粗糙表面结构的Ni-Mo合金在较大的过电位下表现出更好的析氢催化性能,而具有较高Mo含量和细小晶粒尺寸的合金镀层析氢催化活性较高.     

Photo-improved hydrogen evolution reaction activity of the Pt/CdS electrocatalyst

The effect of CdS content on the photo-induced improvement of hydrogen evolution reaction activity of the Pt/CdS electrocatalyst was investigated. Although the electrons transferred from CdS to Pt in the Pt/CdS electrocatalyst increased with the CdS content under illumination, the electrochemical active surface area of the Pt/CdS electrocatalyst decreased with the CdS content, resulting that the photo-induced improvement of hydrogen evolution reaction activity of the Pt/CdS electrocatalyst decreased with the CdS content.     

金属-有机框架材料催化析氧反应的研究进展

面对日益严峻的环境问题,我国提出了“碳中和、碳达峰”的宏伟目标,清洁能源是实现双碳目标的有效手段之一。电解水制氢是一种制备清洁能源的重要方法,然而,电解水过程中析氧反应的缓慢动力学和较高过电位是妨碍水裂解效率的关键因素。金属–有机骨架材料（metal-organic framework,MOF）由于其规整的微观结构、较大的比表面积和可调的孔径等优点,被认为是电解水制氢的优异催化剂。综述了MOF材料用于催化析氧反应的最新研究进展,分析了该类材料的设计策略和催化机制。系统归纳了MOF基催化剂的各种调制策略,包括结晶度调制、电子调制、缺陷调制以及形态调制,并且对MOF材料作为析氧反应催化剂面临的挑战和机遇做出了展望。     

泡沫镍基Ni-S-Co涂层电极在碱性介质中的电催化析氢性能

以泡沫镍为基体采用电沉积法制备非晶态Ni-S-Co合金涂层电极。以扫描电镜(SEM)和X射线衍射(XRD)观察表面形貌和微观结构,电化学测试方法分析涂层的电化学行为。结果表明,所获得的镀层为非晶态结构,表面颗粒细小且具有丰富的表面积;非晶态Ni-S-Co合金电极的析氢催化性能较好,与Ni和Ni-S电极相比具有较低的析氢过电位、较高的交换电流密度和较低的表观活化能;经过KOH碱溶液活化处理后,镀层表面颗粒变细,活性表面积增加,析氢性能有所增强。     

Advances in electrocatalysts for oxygen evolution reaction of water electrolysis-from metal oxides to carbon nanotubes

The water electrolysis for hydrogen production is constrained by the thermodynamically unfavorable oxygen evolution reaction(OER),which requires input of a large amount of energy to drive the reaction.One of the key challenges to increase the efficiency of the water electrolysis system is to develop highly effective and robust electrocatalysts for the OER.In the past 20–30 years,significant progresses have been made in the development of efficient electrocatalysts,including metal oxides,metal oxide-carbon nanotubes(CNTs) hybrid and metal-free CNTs based materials for the OER.In this critical review,the overall progress of metal oxides catalysts and the role of CNTs in the development of OER catalyst are summarized,and the latest development of new metal free CNTs-based OER catalyst is discussed.     

磷化钴/碳纳米管纳米复合电极材料的电催化制氢性能研究

采用化学气相沉积法,在316L不锈钢基底上原位生长碳纳米管,然后在一定浓度的CoSO_4、NaH_2PO_2、NaOAc混合溶液中,用电化学沉积法在碳纳米管表面负载磷化钴纳米颗粒,得到磷化钴/碳纳米管复合结构。利用SEM、EDS和拉曼光谱,对CoP/CNTs复合材料的形貌、成分及物相组成进行分析;通过阴极极化曲线、交流阻抗等电化学测试,重点考察了复合电极在0.5mol/L H_2SO_4溶液中的电催化析氢性能。结果表明,所制CoP/CNTs复合结构中,CoP呈颗粒状均匀分布在CNTs表面;CoP的引入提高了碳纳米管材料的电催化性能,当沉积圈数为4圈时,所制CoP/CNTs复合电极具有最佳的电催化活性;极化曲线测试表明,该电极在电流密度为10mV·cm~(-2)时的过电位与沉积2圈和6圈的CoP/CNTs复合电极相比,正移了约140 mV和90mV,同时也呈现出良好的循环稳定性。     

Dual elemental modulation in cationic and anionic sites of the multi-metal Prussian blue analogue pre-catalysts for promoted oxygen evolution reaction

Designing advanced electrocatalysts for the oxygen evolution reaction (OER) is of great significance owing to its crucial role in facilitating the production of clean hydrogen energy via water splitting. To date, it has been widely accepted that a pre-oxidation process with the in-situ generation of the catalytically active high-valence metal sites is essential for promoting the OER behavior of most transition-metal-based OER catalysts, or more felicitously speaking, pre-catalysts. Hence, exploring such pre-catalysts with high pre-oxidation reactivity is of high promise. Herein, we proposed the dual elemental modulation in the cationic and anionic sites of the multi-metal Prussian blue analogue (PBA) pre-catalysts, resulting in promoted OER behavior benefitted from the efficient pre-oxidation ability as well as the multi-metal synergy. Detailed investigations indicate that the Co-containing multi-metallic cations and mixed Fe^IIICo^III cyanide anions in NiCuCo^II–Fe^IIICo^III PBA (denoted as NiCuCo^II–Fe^IIICo^III) are beneficial to OER catalysis owing to the high intrinsic activity guaranteed by the local Co³⁺ active sites as well as the optimal multi-metal synergy. After the facile pre-oxidation process, additional high-valence Ni, Cu and Fe ions can be in-situ formed and serve as the active sites, thereby resulting in significantly improved OER behavior. For example, the OER current density of NiCuCo^II–Fe^IIICo^III exhibits 1.81 times enhancement even after 72 ?h continuous OER catalysis, and the required overpotential for 10 ?mA ?cm^?2 reduces from 288 ?mV for the fresh pre-catalyst to a remarkable record of 251 ?mV after the pre-oxidation-induced activation, making the optimal PBA-based catalyst a promising candidate for efficient and durable water electrolysis.     

金属有机骨架衍生的NiFe2O4/Co9S8复合催化剂的合成及其电催化析氧性能

以金属有机骨架(metal-organic frameworks, MOFs)化合物为前驱体, 通过退火、硫化等后续处理方法成功制备了由 NiFe₂O₄ 纳米棒与 Co₉S₈ 空心球组装而成的杂化纳米结构. 该复合催化剂因具有较大的比表面积以及各组分间强力的协同作用, 在电催化析氧反应(oxygen evolution reaction, OER)中表现出了优异的催化活性. 在 1 mol/L KOH 电解质中, 当电流密度达到 10 mA/cm² 时, 仅需 290 mV 的过电位, 且 Tafel 斜率仅为 63.02 mV/dec. 此外, 1 000 次循环伏安(cyclic voltammetry, CV)测试后仍然具有良好的催化活性, 表明该复合催化剂具有优异的稳定性. 研究成果不仅为设计廉价、高效且稳定的析氧催化剂提供了设计思路, 也为其他新型纳米复合材料的合成和应用奠定了基础.