层状双金属氢氧化物及其复合材料加速电解水制氢的研究进展

随着经济社会的不断发展和能源的不断消耗,开发清洁能源已引起研究者们的广泛关注。层状双金属氢氧化物(LDH)具有典型的层状结构、制备难度低、组成易调节等优点,在电催化分解水方面表现出可与贵金属催化剂相媲美的性能。目前LDH催化剂仍然存在稳定性不足、活性位点辨别不明、电催化反应机理模糊不清等科学问题亟待解决。本文首先介绍了LDH材料的性质和制备方法,重点从元素和化合物对LDH材料结构和性能的调控、取代阳极OER以及海水氧化三个方面综述了LDH材料在电催化制氢方面的研究进展,阐述了LDH复合材料的形貌、界面作用及化合物之间的协同作用。最后对LDH材料更深层次的研究方向作出展望。     

硫掺杂镍铁层状双氢氧化物的氧析出电催化性能

氧析出反应(OER)是裂解水、二氧化碳还原、以及可充电的锌空电池等许多技术中重要的半反应,但受限于其迟缓的反应动力学,开发高效的氧析出催化剂迫在眉睫.在OER出反应中,性能较好的非贵金属催化剂主要是第四周期过渡金属的一些化合物,如氧化物、氢氧化物、硫化物、硒化物、磷化物等等.在这些材料中,镍铁双金属化合物被认为是最优的氧析出材料,尤其是镍铁层状双氢氧化物(Ni Fe-LDHs)它拥有较大的电化学活性面积以暴露较多活性位点,同时镍铁两种过渡金属元素存在协同效应,使得其具有良好的催化性能.然而,这一类材料的OER性能仍然有优化的空间.研究表明,将硫化物氧化得到的氢氧化物会有少量的硫元素残留,这种硫残留的氢氧化物拥有十分优异的OER性能.为了进一步认识硫的引入对Ni Fe-LDHs的OER行为的影响,本文通过水热法合成了硫掺杂的Ni Fe-LDHs,考察了硫的掺杂量对催化剂性能的影响,验证了微量硫的存在对Ni Fe-LDHs的OER性能的贡献.扫描电镜图片显示,水热合成的催化剂是厚度为几十纳米的薄片,拥有较高的比表面积, X射线荧光光谱分析证明合成的硫掺杂Ni Fe-LDHs中镍铁的元素比例为4:1,而且硫的掺杂量并不影响催化剂的形貌和其中镍铁元素比.X射线光电子能谱分析表明,硫原子的引入使得铁原子结合能降低,即硫与铁的相互作用部分降低了铁的价态,这种硫和铁的相互作用能够优化OER反应中间体OH*与O*在铁活性位点上的吸附自由能,降低氧析出反应的过电势.电化学测试表明,拥有0.43%的硫掺杂Ni Fe-LDHs拥有最好的氧析出性能, 10 m A cm^-1下超电势仅有257 m V, Tafel斜率61.5 m V dec^-1.此后,随着硫掺杂量的提升,其性能先保持稳定,随后有所下降.在稳定测试中,硫掺杂的镍铁层状双氢氧化物在10 m Acm-1电流密度下循环30 h后过电位仅衰减14 m V.在对稳定性测试后的催化剂进行表征表明,催化剂发生了轻微了变形,但这对性能的影响不大.综上,本文提供了一种简便的通过非金属元素掺杂调控过渡金属氧化物的结构和电子态的方法,有望为设计高活性OER电催化剂提供新思路.     

硼、磷共掺杂铁钴双金属材料的制备及其电催化析氧性能

采用一步水热法合成了硼、磷共掺杂铁钴材料(Fe-Co-B-P)。借助扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FT-IR)等技术对所合成材料的形貌、结构和组成进行表征。利用线性扫描伏安(LSV)、循环伏安(CV)、电化学阻抗谱(EIS)等技术研究材料电化学析氧反应(OER)性能。结果表明,Fe-Co-B-P表面疏松且粗糙,颗粒间有许多空隙。在电流密度为10和100 mA·cm^-2时,其过电势分别为278和309 mV,Tafel斜率为24 mV·dec^-1,说明该材料具有较优的电催化析氧性能。其在连续进行10 h的计时电位测试过程中,电势基本保持在1.55 V(vs RHE),表明该催化剂具有较好的电化学稳定性。这是由于铁钴双金属与硼、磷非金属之间的协同作用促进了电子的传递。     

硼、磷共掺杂铁钴双金属材料的制备及其电催化析氧性能

采用一步水热法合成了硼、磷共掺杂铁钴材料(Fe-Co-B-P)。借助扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FT-IR)等技术对所合成材料的形貌、结构和组成进行表征。利用线性扫描伏安(LSV)、循环伏安(CV)、电化学阻抗谱(EIS)等技术研究材料电化学析氧反应(OER)性能。结果表明，Fe-Co-B-P表面疏松且粗糙，颗粒间有许多空隙。在电流密度为10和100 mA·cm^-2时，其过电势分别为278和309 mV，Tafel斜率为24 mV·dec^-1，说明该材料具有较优的电催化析氧性能。其在连续进行10 h的计时电位测试过程中，电势基本保持在1.55 V (vs RHE)，表明该催化剂具有较好的电化学稳定性。这是由于铁钴双金属与硼、磷非金属之间的协同作用促进了电子的传递。     

硫掺杂镍铁层状双氢氧化物的氧析出电催化性能（英文）

氧析出反应(OER)是裂解水、二氧化碳还原、以及可充电的锌空电池等许多技术中重要的半反应,但受限于其迟缓的反应动力学,开发高效的氧析出催化剂迫在眉睫.在OER出反应中,性能较好的非贵金属催化剂主要是第四周期过渡金属的一些化合物,如氧化物、氢氧化物、硫化物、硒化物、磷化物等等.在这些材料中,镍铁双金属化合物被认为是最优的氧析出材料,尤其是镍铁层状双氢氧化物(Ni Fe-LDHs)它拥有较大的电化学活性面积以暴露较多活性位点,同时镍铁两种过渡金属元素存在协同效应,使得其具有良好的催化性能.然而,这一类材料的OER性能仍然有优化的空间.研究表明,将硫化物氧化得到的氢氧化物会有少量的硫元素残留,这种硫残留的氢氧化物拥有十分优异的OER性能.为了进一步认识硫的引入对Ni Fe-LDHs的OER行为的影响,本文通过水热法合成了硫掺杂的Ni Fe-LDHs,考察了硫的掺杂量对催化剂性能的影响,验证了微量硫的存在对Ni Fe-LDHs的OER性能的贡献.扫描电镜图片显示,水热合成的催化剂是厚度为几十纳米的薄片,拥有较高的比表面积, X射线荧光光谱分析证明合成的硫掺杂Ni Fe-LDHs中镍铁的元素比例...     

泡沫镍原位负载双金属AlCo层状双氢氧化物纳米催化剂高效电催化析氧反应

经一步水热法在泡沫镍（NF）上原位生长获得了AlCo-LDH/NF （LDH=层状双氢氧化物）催化剂。基于AlCo-LDH的高表面积和良好相界面,催化剂表现出了优异的电催化析氧反应（OER）活性。在碱性介质中,当电流密度为200 mA·cm^-2时,AlCo₃-LDH/NF催化剂具有419 mV的低过电位和50.04 mV·dec^-1的低Tafel斜率。     

用于电催化析氧反应电极的制备策略

随着能源枯竭和环境污染等问题的日益严重,开发清洁可再生能源及相关新型技术迫在眉睫。近年来,水分解、金属-空气电池等电化学能源储存和转换技术得到人们的广泛关注。电催化析氧反应(Oxygen evolution reaction,OER)是其中的一个关键反应,大量高性能的OER电催化剂不断见诸报道。除了材料本征催化活性的影响,不同的电极制备方式同样会对催化剂性能的发挥起到重要作用,越来越多的研究者致力于探索高效OER电极的设计与制备方法。本综述从方法论的角度,详细介绍了目前高效OER电极的制备策略,讨论了各类制备方式的优势和不足,总结了相关工作的最新研究进展,概述了新型电极的制备方法。最后,对电极制备策略的发展方向进行了总结与展望。     

二维石墨炔/金属氢氧化物异质结用于高效析氧反应

析氧反应(OER)是能量转换过程中重要的半反应,开发高效、稳定、低成本的析氧反应催化剂具有重要的意义.本文报道了 一种简单的原位可控生长的方法,在铜双金属氢氧化物纳米片表面原位生长石墨炔薄膜,形成了新型石墨炔/金属氢氧化物异质结界面结构,并通过改变化学组成的方法,实现对其电催化OER活性和稳定性的有效提升.研究结果显示...     

双金属氢氧化物催化析氧反应的协同机制研究

双金属氢氧化物(LDH)是催化析氧反应(OER)活性最佳的一类催化剂,其中揭示双金属位点的协同作用是进一步提升其电催化、光催化性能的关键.本工作采用密度泛函方法,从理论计算角度探究了五种M32+N3+-LDH(M2+=Co2+、Ni2+,N3+=Al3+、Cr3+、Mn3+、Fe3+)在催化OER中的反应机制和双金属位...     

氮掺杂碳纤维负载镍钴硒化物的制备及其电催化析氢性能

以静电纺丝制备的纤维为前驱体,通过煅烧、硒化处理等工艺合成了负载双金属硒化物纳米粒子的氮掺杂碳纤维(NCF)材料((Ni,Co)Se2/NCF),并对其进行了一系列相关的表征,研究了其在酸性和碱性条件下的析氢性能.(Ni,Co)Se2纳米粒子被锚定于NCF中,有效地阻止了纳米粒子的聚集,提供了更多的催化活性位点.电催化...     

A Strongly Coupled Graphene and FeNi Double Hydroxide Hybrid as an Excellent Electrocatalyst for the Oxygen Evolution Reaction

Cost‐effective electrocatalysts for the oxygen evolution reaction (OER) are critical to energy conversion and storage processes. A novel strategy is used to synthesize a non‐noble‐metal‐based electrocatalyst of the OER by finely combining layered FeNi double hydroxide that is catalytically active and electric conducting graphene sheets, taking advantage of the electrostatic attraction between the two positively charged nanosheets. The synergy between the catalytic activity of the double hydroxide and the enhanced electron transport arising from the graphene resulted in superior electrocatalytic properties of the FeNi‐GO hybrids for the OER with overpotentials as low as 0.21 V, which was further reduced to 0.195 V after the reduction treatment. Moreover, the turnover frequency at the overpotential of 0.3 V has reached 1 s^?1, which is much higher than those previously reported for non‐noble‐metal‐based electrocatalysts.     

Nickel-Based Metal-Organic Frameworks as Electrocatalysts for the Oxygen Evolution Reaction (OER)

The exploration of earth-abundant electrocatalysts with high performance for the oxygen evolution reaction (OER) is eminently desirable and remains a significant challenge. The composite of the metal-organic framework (MOF) Ni₁₀Co-BTC (BTC = 1,3,5-benzenetricarboxylate) and the highly conductive carbon material ketjenblack (KB) could be easily obtained from the MOF synthesis in the presence of KB in a one-step solvothermal reaction. The composite and the pristine MOF perform better than commercially available Ni/NiO nanoparticles under the same conditions for the OER. Activation of the nickel-cobalt clusters from the MOF can be seen under the applied anodic potential, which steadily boosts the OER performance. Ni₁₀Co-BTC and Ni₁₀Co-BTC/KB are used as sacrificial agents and undergo structural changes during electrochemical measurements, the stabilized materials show good OER performances.     

镍铁水滑石电催化氧析出研究进展

氧析出反应(Oxygen evolution reaction, OER)是电解水制氢、二氧化碳还原、二次金属-空气电池等能源储存和转化技术中的关键半反应。镍铁水滑石类材料(NiFe layered double hydroxide, NiFe-LDH)具有独特的层状结构、优异的催化性能和成本低廉等优点,是一类极具潜力的OER催化材料。但电导率低、活性位点暴露不充分等缺点也限制了其催化性能的进一步提高。本文综述了包括引入缺陷、片层剥离、元素掺杂、表面修饰和原位生长等针对NiFe-LDH的改性方法,这些方法能有效提升反应活性位点数量、增强导电性并促进反应动力学过程。最后,讨论了对NiFe-LDH改性中存在的问题以及对后续研究的展望。     

Electrodeposition of Defect-Rich Ternary NiCoFe Layered Double Hydroxides: Fine Modulation of Co3+ for Highly Efficient Oxygen Evolution Reaction

The low-cost, high-abundance and durable layered double hydroxides (LDHs) have been considered as promising electrocatalysts for oxygen evolution reaction (OER). However, the easy agglomeration of lamellar LDHs in the aqueous phase limits their practical applications. Herein, a series of ternary NiCoFe LDHs were successfully fabricated on nickel foam (NF) via a simple electrodeposition method. The as-prepared Ni(Co_0.5Fe_0.5)/NF displayed an unique nanoarray structural feature. It showed an OER overpotential of 209 mV at a current density of 10 mA cm⁻² in alkaline solution, which was superior to most systems reported so far. As evidenced by the XPS and XAFS results, such excellent performance of Ni(Co_0.5Fe_0.5)/NF was attributed to the higher Co³⁺/Co²⁺ ratio and more defects exposed, comparing with Ni(Co_0.5Fe_0.5)-bulk and Ni(Co_0.5Fe_0.5)-mono LDHs prepared by conventional coprecipitation method. Furthermore, the ratio of Co to Fe could significantly tune the Co electronic structure of Ni(Co_xFe_1-x)/NF composites (x=0.25, 0.50 and 0.75) and affect the electrocatalytic activity for OER, in which Ni(Co_0.5Fe_0.5)/NF showed the lowest energy barrier for OER rate-determining step (from O* to OOH*). This work proposes a facile method to develop high-efficiency OER electrocatalysts.     

镍铁水滑石/还原氧化石墨烯的制备及电催化水氧化性能

首先制备了不同镍/铁比的镍铁水滑石, 并通过液相剥离法得到水滑石纳米薄片溶胶, 随后将其与还原氧化石墨烯复合, 并对其进行了电催化水氧化的性能测试. 结果表明, 镍铁水滑石的剥离可以大幅度提高其电催化性能, 起峰电位为1.47 V, 电流密度为10 mA/cm² 时, 电位仅为1.53 V; 与还原氧化石墨烯复合后, 其催化活性得到了进一步提高, 在10 mA/cm²时电位降为 1.515 V.     

Bifunctional Catalysts for Reversible Oxygen Evolution Reaction and Oxygen Reduction Reaction

Metal-air batteries (MABs) and reversible fuel cells (RFCs) rely on the bifunctional oxygen catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Finding efficient bifunctional oxygen catalysts is the ultimate goal and it has attracted a great deal of attention. The dilemma is that a good ORR catalyst is not necessarily efficient for OER, and vice versa. Thus, the development of a new type of bifunctional oxygen catalysts should ensure that the catalysts exhibit high activity for both OER and ORR. Composites with multicomponents for active centers supported on highly conductive matrices could be able to meet the challenges and offering new opportunities. In this Review, the evolution of bifunctional catalysts is summarized and discussed aiming to deliver high-performance bifunctional catalysts with low overpotentials.     

Introducing Fe2+ into Nickel–Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Herein we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe‐LDHs) by partially substituting Ni²⁺ with Fe²⁺ to introduce Fe‐O‐Fe moieties. These Fe²⁺‐containing NiFe‐LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA cm^?2, which is among the best OER catalytic performance to date. In‐situ X‐ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe‐O‐Fe motifs could stabilize high‐valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.     

Preparation of Quaternary FeCoMoCu Metal Oxides for Oxygen Evolution Reaction

Molybdenum doping is an effective way to improve the oxygen evolution reaction(OER) properties of catalysts, which can efficiently improve the electronic conductivity, mass transport process, and intrinsic activity of transition metal oxides or hydroxides, especially for those multi-component oxides with more abundant active sites. Herein, we have prepared a quaternary FeCoMoCu metal oxide on Cu foam(FeCoMoCuO_x@Cu) as an efficient OER catalyst. As expected, FeCoMoCuO_x@Cu could exhibit a low overpotential(252 mV at the current density of 10 mA/cm²) and exceptional stability(10000 cycles of CV scans or constant electrolysis for 48 h).