A Roadmap to Low‐Cost Hydrogen with Hydroxide Exchange Membrane Electrolyzers

Hydrogen is an ideal alternative energy carrier to generate power for all of society's energy demands including grid, industrial, and transportation sectors. Among the hydrogen production methods, water electrolysis is a promising method because of its zero greenhouse gas emission and its compatibility with all types of electricity sources. Alkaline electrolyzers (AELs) and proton exchange membrane electrolyzers (PEMELs) are currently used to produce hydrogen. AELs are commercially mature and are used in a variety of industrial applications, while PEMELs are still being developed and find limited application. In comparison with AELs, PEMELs have more compact structure and can achieve higher current densities. Recently, however, an alternative technology to PEMELs, hydroxide exchange membrane electrolyzers (HEMELs), has gained considerable attention due to the possibility to use platinum group metal (PGM)‐free electrocatalysts and cheaper membranes, ionomers, and construction materials and its potential to achieve performance parity with PEMELs. Here, the state‐of‐the‐art AELs and PEMELs along with the current status of HEMELs are discussed in terms of their positive and negative aspects. Additionally discussed are electrocatalyst, membrane, and ionomer development needs for HEMELs and benchmark electrocatalysts in terms of the cost–performance tradeoff.     

水热合成镍铜复合磷化物及其电催化析氢与肼氧化性能

以镍网(NM, Nickel Mesh)为基体、NaH₂PO₂·H₂O为磷源、CuSO₄·5H₂O为铜源、NiSO₄·6H₂O为镍源, 采用一步水热法合成镍铜磷复合电催化剂, 对制备工艺进行优化, 并通过不同方法进行形貌、结构、组成和电催化性能表征。结果表明：当溶液中镍、铜、磷的配比为8: 1 :20时, 在140 ℃水热合成24 h, 制得主晶相为Ni₂P和Cu₃P、具有三级微纳结构的镍铜磷复合电催化剂。在电流密度为10 mA·cm ^-2时, NiCuP/NM的催化析氢及肼氧化过电势分别为165和49 mV; 在双电极体系中, 同电流密度下的分解槽压仅为0.750 V, 催化24 h后分解槽压几乎保持不变, 展现出优异的催化稳定性。无论三电极体系还是双电极体系均表现出优异的催化活性。分析认为, 电催化活性面积为空白镍网的近14倍, 为电催化过程提供了大量的活性位点; 掺入P改变了Ni、Cu原子的电子结构, 提高了材料的本征肼氧化活性, 两者的协同作用促进了电催化活性的提升。本研究为纳米尺度的合成提供了一个新的视角, 有望推动新型纳米孔结构材料在燃料电池和传感器应用中的发展。     

A Porous Perovskite Nanofiber with Reinforced Aerophobicity for High-Performance Anion Exchange Membrane Water Splitting

Perovskite oxides stand out as emerging oxygen evolution reaction (OER) catalysts on account of their effective electrocatalytic performance and low costs. Nevertheless, perovskite oxides suffer from severe bubble overpotential and inhibited electrochemical performance in large current densities due to their small specific surface areas and structural compactness. Herein, the study highlights the electrospun nickel-substituted La_0.5Sr_0.5FeO_3-δ (LSF) porous perovskite nanofibers, that is, La_0.5Sr_0.5Fe_1-xNi_xO_3-δ (denoted as ES-LSFN-x, x = 0, 0.1, 0.3, and 0.5), as high-performance OER electrocatalysts. The most effective La_0.5Sr_0.5Fe_0.5Ni_0.5O_3-δ (ES-LSFN-0.5) nanofibers suggest a larger specific surface area, higher porosity, and faster mass transfer than the counterpart sample prepared by conventional sol–gel method (SG-LSFN-0.5), showing notably increased geometric and intrinsic activities. The bubble visualization results demonstrate that the enriched and nano-sized porosity of ES-LSFN-0.5 enables reinforced aerophobicity and rapid detachment of oxygen bubbles, thereby reducing the bubble overpotential and enhancing the electrochemical performance. As a result, the ES-LSFN-0.5-based anion exchange membrane water electrolysis delivers a superior stability of 100 h while the SG-LSFN-0.5 counterpart degrades rapidly within 20 h under a current density of 100 mA cm⁻². The results highlight the advantage of porous electrocatalysts in optimizing the performance of large current density water electrolysis devices by reducing the bubble overpotential.     

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.     

Encapsulating Ni Nanoparticles into Interlayers of Nitrogen-Doped Nb2CTx MXene to Boost Hydrogen Evolution Reaction in Acid

Design and development of low-cost and highly efficient non-precious metal electrocatalysts for hydrogen evolution reaction (HER) in an acidic medium are key issues to realize the commercialization of proton exchange membrane water electrolyzers. Ni is regarded as an ideal alternative to substitute Pt for HER based on the similar electronic structure and low price as well. However, low intrinsic activity and poor stability in acid restrict its practical applications. Herein, a new approach is reported to encapsulate Ni nanoparticles (NPs) into interlayer edges of N-doped Nb₂CT_x MXene (Ni NPs@N-Nb₂CT_x) by an electrochemical process. The as-prepared Ni NPs@N-Nb₂CT_x possesses Pt-like onset potentials and can reach 500 mA cm⁻² at overpotentials of only 383 mV, which is much higher than that of N-Nb₂CT_x supported Ni NPs synthesized by a wet-chemical method (w- Ni NPs/N-Nb₂CT_x). Furthermore, it shows high durability toward HER with a large current density of 300 mA cm⁻² for 24 h because of the encapsulated structure against corrosion, oxidation as well as aggregation of Ni NPs in an acidic medium. Detailed structural characterization and density functional theory calculations reveal that the stronger interaction boosts the HER.     

季铵化壳聚糖/[Nbmm]OH碱性复合阴离子膜的制备及性能

以季铵化壳聚糖(QCS)为制膜原料,[Nbmm]OH碱性离子液体为掺杂物,通过溶液浇铸法制备了一系列掺杂碱性离子液体([Nbmm]OH)的交联复合膜(QCS/[Nbmm]OH)。采用红外光谱、热重分析及扫描电镜对复合膜的结构、热稳定性和微观形貌进行分析。同时考察离子液体掺杂量对QCS/[Nbmm]OH复合膜的含水率、力学强度及导电性能等指标的影响。结果表明,随着[Nbmm]OH离子液体掺杂量的增加,复合膜的含水率、离子交换量以及电导率均增加,但是拉伸强度和断裂伸长率略有下降。其中,当离子液体掺杂量为15%(质量分数)时,复合膜在70℃的电导率为0.0115S/cm,拉伸强度为19 MPa,离子交换量为1.25 mmol/g,含水率和溶胀度分别为143%和87%。     

镍合金析氢电极研究概述

从镍合金析氢电极的分类、性能、表征、析氢机理、催化机理以及工业化应用前景等方面对该电极的研究状况进行了简要的评述与分析.     

Guanidine分子在燃料电池用阴离子交换膜中的应用

以壳聚糖(CS)和2,3-环氧丙基三甲基氯化铵(GTA)为原料,制备季铵化壳聚糖(QCS),将其与小分子游离胍(Guanidine)共混,借助戊二醛(GA)的化学交联作用,将季铵化壳聚糖中的氨基以及胍中的氨基交联,形成网状结构,由此制得含有不同含量Guanidine分子的交联QCS-G阴离子交换膜。实验过程中,对该膜的含水率、溶胀度、力学强度、电导率及耐碱稳定性等进行了详细的考察。结果表明,游离胍的引入可有效地提高膜的电导率和耐碱稳定性,同时降低了膜的溶胀度及含水率。其中小分子游离胍质量分数为2.5%的膜(QCS-G2.5%)在70℃时的电导率可达到6.58×10~(-2)S/cm;在10 mol/L NaOH溶液中浸渍72 h后该膜70℃测得的电导率损失仅为3.8%,离子交换量损失仅为3.82%,表明该膜的耐碱性能较好。     

Hydroxyapatite-Derived Heterogeneous Ru-Ru2P Electrocatalyst and Environmentally-Friendly Membrane Electrode toward Efficient Alkaline Electrolyzer

Alkaline membrane water electrolysis is a promising production technology, and advanced electrocatalyst and membrane electrode design have always been the core technology. Herein, an ion-exchange method and an environmentally friendly in situ green phosphating strategy are successively employed to fabricate Ru-Ru₂P heterogeneous nanoparticles by using hydroxyapatite (HAP) as a phosphorus source, which is an exceptionally active electrocatalyst for hydrogen evolution reaction (HER). Density functional theory calculation results reveal that strong electronic redistribution occurs at the heterointerface of Ru-Ru₂P, which modulates the electronic structure to achieve an optimized hydrogen adsorption strength. The obtained Ru-Ru₂P possesses excellent HER performance (24 mV at 10 mA cm⁻²) and robust stability (1000 mA cm⁻² for 120 h) in alkaline media. Furthermore, an environmentally friendly membrane electrode with a sandwich structure is assembled by HAP nanowires as an alkaline membrane, Ru-Ru₂P as a cathodic catalyst, and NiFe-LDH as an anodic catalyst, respectively. The voltage of (−) Ru-Ru₂P || NiFe-LDH/CNTs (+) (1.53 V at 10 mA cm⁻²) is lower than that of (−) 20 wt% Pt/C || RuO₂ (+) (1.60 V at 10 mA cm⁻²) for overall water splitting. Overall, the studies not only design an efficient catalyst but also provide a new route to achieve a high-stability electrolyzer for industrial H₂ production.     

Optimizing the Electronic Structure of Atomically Dispersed Ru Sites with CoP for Highly Efficient Hydrogen Evolution in both Alkaline and Acidic Media

Developing efficient and stable electrocatalysts for hydrogen evolution reaction (HER) over a wide pH range and industrial large-scale hydrogen production is critical and challenging. Here, a tailoring strategy is developed to fabricate an outstanding HER catalyst in both acidic and alkaline electrolytes containing high-density atomically dispersed Ru sites anchored in the CoP nanoparticles supported on carbon spheres (NC@Ru_SA-CoP). The obtained NC@Ru_SA-CoP catalyst exhibits excellent HER performance with overpotentials of only 15 and 13 mV at 10 mA cm⁻² in 1 m KOH and 0.5 m H₂SO₄, respectively. The experimental results and theoretical calculations indicate that the strong interaction between the Ru site and the CoP can effectively optimize the electronic structure of Ru sites to reduce the hydrogen binding energy and the water dissociation energy barrier. The constructed alkaline anion exchange membrane water electrolyze (AAEMWE) demonstrates remarkable durability and an industrial-level current density of 1560 mA cm⁻² at 1.8 V. This strategy provides a new perspective on the design of Ru-based electrocatalysts with suitable intermediate adsorption strengths and paves the way for the development of highly active electrocatalysts for industrial-scale hydrogen production.     

Interfacial Engineering of Polycrystalline Pt5P2 Nanocrystals and Amorphous Nickel Phosphate Nanorods for Electrocatalytic Alkaline Hydrogen Evolution

Electrocatalytic hydrogen evolution reaction (HER) in alkaline media is important for hydrogen economy but suffers from sluggish reaction kinetics due to a large water dissociation energy barrier. Herein, Pt₅P₂ nanocrystals anchoring on amorphous nickel phosphate nanorods as a high-performance interfacial electrocatalyst system (Pt₅P₂ NCs/a-NiPi) for the alkaline HER are demonstrated. At the unique polycrystalline/amorphous interface with abundant defects, strong electronic interaction, and optimized intermediate adsorption strength, water dissociation is accelerated over abundant oxophilic Ni sites of amorphous NiPi, while hydride coupling is promoted on the adjacent electron-rich Pt sites of Pt₅P₂. Meanwhile, the ultra-small-sized Pt₅P₂ nanocrystals and amorphous NiPi nanorods maximize the density of interfacial active sites for the Volmer–Tafel reaction. Pt₅P₂ NCs/a-NiPi exhibits small overpotentials of merely 9 and 41 mV at −10 and −100 mA cm⁻² in 1 M KOH, respectively. Notably, Pt₅P₂ NCs/a-NiPi exhibits an unprecedentedly high mass activity (MA) of 14.9 mA µg_Pt⁻¹ at an overpotential of 70 mV, which is 80 times higher than that of Pt/C and represents the highest MA of reported Pt-based electrocatalysts for the alkaline HER. This work demonstrates a phosphorization and interfacing strategy for promoting Pt utilization and in-depth mechanistic insights for the alkaline HER.     

水分解制氢的光触媒陶瓷材料研究进展

利用自然光能使水分解制氢是解决能源短缺和环境污染的最好办法，光触媒材料可将光能转变为化学能，其应用前景十分广阔。详细叙述了光触媒催化作用的原理、光解媒材料的近期研究成果，并提出了光触媒材料今后主要应解决的关键问题。     

含咪唑聚离子液体的星型POSS嵌段共聚物基阴离子交换膜的制备与性能

以聚甲基丙烯酸甲酯嵌段聚乙烯基咪唑为臂,低聚倍半硅氧烷(POSS)为核的星型嵌段共聚物POSS-(PMMA-bPVIm)8为基膜材料,通过季铵化反应和离子交换过程对其进行改性,制备2种咪唑聚离子液体嵌段不同的阴离子交换膜,分别记作PMV-1、PMV-2,研究其吸水率、溶胀度、离子交换容量、力学性能、电导率及耐碱性。结果表明,膜在90℃时仍保持适当的吸水强度,2种膜的吸水率分别为18.09%和25.81%,厚度方向溶胀度分别为25.31%,35.45%;30℃时PMV-1、PMV-2的离子交换容量分别为2.38 meq/g,3.12 meq/g,力学性能良好;2种膜室温下均已具有良好的离子传输性能,90℃时电导率分别达44.02 m S/cm和255.0 m S/cm;耐碱性测试表明,含聚离子液体嵌段较短的膜PMV-1稳定性较好,60℃强碱溶液中浸泡120 h后电导率下降不超过30%。     

质子交换膜燃料电池水管理动态模型研究

水管理是质子交换膜燃料电池取得良好性能的关键因素之一,膜中水的含量及其分布的不均匀造成了电池性能下降。限于试验条件及测试技术,为了更好地探明电池中水的行为及分布,研究者们开展了大量的数学模型和仿真模拟。从质子交换膜燃料电池的工作原理角度出发,回顾了有关质子交换膜中水传递从一维模型到三维模型的发展历程,并阐述了各个阶段研究的要点、限定条件和主要的研究成果。同时,提出了未来水管理方面数学模型和仿真模拟发展的新方向。模型的完善有利于燃料电池控制策略的研究,这将为电池的优化设计提供理论基础。     

Synthesis of Hierarchical 4H/fcc Ru Nanotubes for Highly Efficient Hydrogen Evolution in Alkaline Media

Hierarchical metal nanostructures containing 1D nanobuilding blocks have stimulated great interest due to their abundant active sites for catalysis. Herein, hierarchical 4H/face‐centered cubic (fcc) Ru nanotubes (NTs) are synthesized by a hard template‐mediated method, in which 4H/fcc Au nanowires (NWs) serve as sacrificial templates which are then etched by copper ions (Cu²⁺) in dimethylformamide. The obtained hierarchical 4H/fcc Ru NTs contain ultrathin Ru shells (5–9 atomic layers) and tiny Ru nanorods with length of 4.2 ± 1.1 nm and diameter of 2.2 ± 0.5 nm vertically decorated on the surface of Ru shells. As an electrocatalyst for the hydrogen evolution reaction in alkaline media, the hierarchical 4H/fcc Ru NTs exhibit excellent electrocatalytic performance, which is better than 4H/fcc Au‐Ru NWs, commercial Pt/C, Ru/C, and most of the reported electrocatalysts.     

非晶态Fe-Mo合金在碱性溶液中的电催化析氢活性

研究了电沉积制备的非晶态Fe-Mo合金(组成分别为Fe82Mo18、Fe74Mo26和Fe71Mo29)电极在30％KOH溶液中，303～343K的温度范围内的析氢催化性能。三种非晶态合金都显示出较好的催化析氢活性。温度为343K，析H2电流密度为300nA／cm^2时的析H2过电位为150～157mV。非晶态Fe82Mol8、Fe74Mo26和Fe71Mo29合金上析H2反应的表观活化能分别为57．18，47．33，102．28kJ／mol。     

Boosting Alkaline Hydrogen and Oxygen Evolution Kinetic Process of Tungsten Disulfide-Based Heterostructures by Multi-Site Engineering

Alkaline water electrolysis is an advanced technology for scalable H₂ production using surplus electricity from intermittent energy sources, but it remains challenging for non-noble electrocatalysts to split water into hydrogen and oxygen efficiently, especially for tungsten disulfide (WS₂)-based catalysts. Density functional theory calculations in combination with experimental study are used to establish a multi-site engineering strategy for developing robust WS₂-based hybrid electrocatalyst on mesoporous bimetallic nitride (Ni₃FeN) nanoarrays for bifunctional water splitting. This ingenious design endows the catalyst with numerous edge sites chemically bonded with the conductive scaffold, which are favorable for water dissociation and hydrogen adsorption. Benefiting from the synergistic advantages, the N-WS₂/Ni₃FeN hybrid exhibits exceptional bifunctional properties for hydrogen and oxygen evolution reactions (HER and OER) in base with excellent large-current durability, requiring 84 mV to afford 10 mA cm^?2 for HER, and 240 mV at 100 mA cm^?2 for OER, respectively. Assembling the catalytic materials as both the anode and cathode to construct an electrolyzer, it is actualized very good activities for overall water splitting with only 1.5 V to deliver 10 mA cm^?2, outperforming the IrO₂⁽⁺⁾//Pt^(?) coupled electrodes and many non-noble bifunctional electrocatalysts thus far. This work provides a promising avenue for designing WS₂-based heterogeneous electrocatalysts for water electrolysis.     

Modulating Electronic Environment of Ru Nanoclusters via Local Charge Transfer for Accelerating Alkaline Water Electrolysis

Compared to platinum catalysts, ruthenium (Ru) is disclosed as a promising alternative for alkaline water electrolysis due to its similar hydrogen adsorption energy and relatively lower water dissociation barrier. However, in the challenging alkaline media, the dissatisfied Volmer step during water dissociation of Ru metal prohibits its practical applications. Here, a new pathway to modulate the electronic environment of Ru catalysts via a local charge transfer strategy for tuning the water dissociation kinetics and accelerating the alkaline water electrolysis is proposed. The obtained catalysts are engineered by assembling and subsequently pyrolyzing the layer-stacked and 2D porphyrin-based Ru-N coordination polymers on nanocarbon supports. Benefiting from the well-defined Ru nanocluster-N_x-coordination bonds (Ru_nc-N_x), unique electronic environments, and local charge transfer properties, the catalysts exhibit the exceptional activity of 17 mV overpotential at 10 mA cm⁻² and robust stability in water, which is more efficient than state-of-the-art Ru catalysts. The theoretical calculation suggests that the Ru_nc-N_x sites enhance the nucleophilic attack of water and weaken the H OH bond. This study manifests that tailoring the bond environments of Ru clusters can significantly modulate their intrinsic catalytic activities and stabilities, which may open new avenues for developing high-active and durable catalysts for water electrolysis.     

RuO2/ZrO2/TaON复合光催化材料的制备及光解水制氢性能

采用控制水解法制备了细颗粒的ZrO₂/Ta₂O₅复合氧化物粉体, 在氨气流量为90 mL/min、850℃下氮化10 h获得ZrO₂/TaON, 用浸渍法制备含助催化剂RuO₂的复合光催化剂。用XRD、SEM、TEM和UV-Vis漫反射光谱等对所制备的光催化材料进行了表征, ZrO₂、RuO₂的晶粒尺寸约为10 nm,TaON的晶粒尺寸约为25 nm, 复合光催化剂可以吸收波长≤500 nm的可见光。ZrO₂的引入降低了氮化生成TaON的缺陷密度, 提高了TaON的比表面积。光电流及光催化分解水制氢反应定量评价了复合材料的光催化性能, RuO₂含量为2.0wt%时复合光催化剂活性最高, 0.6 V偏压下光电流密度为0.6 mA/cm², 产氢速率为6.0 μmol/h。