hydroxide

氢氧化物
  • 文章类型: Journal Article
    氢氧化物交换膜燃料电池(HEMFCs)是有前途的,但缺乏高性能的阳极氢氧化反应(HOR)电催化剂。铂族金属(PGMs)在碱性介质中的HOR活性比酸中的HOR活性低2至3个数量级,导致阳极上所需的高PGM量以实现高HEMFC性能。机理研究表明,催化剂的氢结合能决定碱性HOR动力学,和吸附在催化剂表面的OH和水促进HOR。铱(Ir)由于其与Pt相似的氢结合能和增强的OH吸附而对碱性HOR具有独特的优势。然而,在HEMFC的实际应用中,Ir/C的HOR活性仍未得到满足。进一步微调中间体在Ir基催化剂上的吸附对提高其碱性HOR活性具有重要意义,这可以通过结构设计和组成调节来合理实现。在这个概念中,我们解决了当前对碱性HOR机理的理解,并总结了具有增强碱性HOR活性的基于Ir的电催化剂的最新进展。我们还讨论了未来基于Ir的电催化剂的前景和挑战。
    The hydroxide exchange membrane fuel cells (HEMFCs) are promising but lack of high-performance anode hydrogen oxidation reaction (HOR) electrocatalysts. The platinum group metals (PGMs) have the HOR activity in alkaline medium two to three orders of magnitude lower than those in acid, leading to the high required PGMs amount on anode to achieve high HEMFC performance. The mechanism study demonstrates the hydrogen binding energy of the catalyst determines the alkaline HOR kinetics, and the adsorbed OH and water on the catalyst surface promotes HOR. Iridium (Ir) has a unique advantage for alkaline HOR due to its similar hydrogen binding energy to Pt and enhanced adsorption of OH. However, the HOR activity of Ir/C is still unsatisfied in practical HEMFC applications. Further fine tuning the adsorption of the intermediate on Ir-based catalysts is of great significance to improve their alkaline HOR activity, which can be reasonably realized by structure design and composition regulation. In this concept, we address the current understanding about the alkaline HOR mechanism and summarize recent advances of Ir-based electrocatalysts with enhanced alkaline HOR activity. We also discuss the perspectives and challenges on Ir-based electrocatalysts in the future.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

    求助全文

  • 文章类型: Journal Article
    高度期望先进的光催化剂以低浓度活化光催化CO2还原反应(CO2RR)。在这里,合成了具有丰富表面晶格羟基的NiSn(OH)6,以直接在自然空气中增强活性。结果表明,末端Ni-OH可以作为供体供给质子并产生氧空位(VO),从而有利于将大气中的活化CO2(HCO3-)主要转化为CO(5.60μmol/g)。它是灵活的,广泛适用于从高纯到空气水平的稳定的CO2RR,没有额外添加H2O反应物,高于传统的气-液-固(1.58μmol/g)和气-固(4.07μmol/g)反应体系,均使用高纯CO2和大量H2O。丰富的表面羟基的强亲水性使H2O分子在VO位点的强大吸附和解离实现Ni-OH再生,无论空气中的CO2和H2O含量如何,富含可再生VO都会导致稳定的CO产量(11.61μmol/g)。这项工作为自然光合作用的实际应用开辟了新的可能性。
    Advanced photocatalysts are highly desired to activate the photocatalytic CO2reduction reaction (CO2RR) with low concentration. Herein, the NiSn(OH)6with rich surface lattice hydroxyls was synthesized to boost the activity directly under the natural air. Results showed that terminal Ni-OH could serve as donors to feed protons and generate oxygen vacancies (VO), thus beneficial to convert the activated CO2(HCO3-) mainly into CO (5.60μmol g-1) in the atmosphere. It was flexible and widely applicable for a stable CO2RR from high pure to air level free of additionally adding H2O reactant, and higher than the traditional gas-liquid-solid (1.58μmol g-1) and gas-solid (4.07μmol g-1) reaction system both using high pure CO2and plenty of H2O. The strong hydrophilia by the rich surface hydroxyls allowed robust H2O molecule adsorption and dissociation at VOsites to achieve the Ni-OH regeneration, leading to a stable CO yield (11.61μmol g-1) with the enriched renewable VOregardless of the poor CO2and H2O in air. This work opens up new possibilities for the practical application of natural photosynthesis.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

    求助全文

  • 文章类型: Journal Article
    氢氧化物是具有金属-氧(M-O)八面体单元的层状晶体的原型,已被广泛研究作为析氧反应(OER)催化剂。然而,氢氧化物材料的结晶度越好,更完美的八面体对称性和原子有序,导致较少的暴露金属位点和有限的电催化活性。在这里,开发了具有短程有序和长程无序结构的玻璃态氢氧化物材料以实现OER的高固有活性。具体来说,利用快速冰点沉淀法制备无定形多组分氢氧化物。由于冰点结晶环境和混乱的M-O(M=Ni/Fe/Co/Mn/Cr等)。)结构,制造的NiFeCoMnCr氢氧化物表现出高度无序的玻璃态结构,通过X射线/电子衍射证实,焓响应,和成对分布函数分析。获得的玻璃态氢氧化物材料在20mAcm-2时显示出269mV的低OER超电势,Tafel斜率为33.3mVdec-1,优于基准贵金属RuO2催化剂(341mV,84.9mVdec-1)。操作拉曼和密度泛函理论研究表明,在低OER超电势下,玻璃态氢氧化物以优化的氧中间体吸附转化为无序的活性羟基氧化物相,从而增强内在的电催化活性。
    Hydroxides are the archetype of layered crystals with metal-oxygen (M-O) octahedron units, which have been widely investigated as oxygen evolution reaction (OER) catalysts. However, the better crystallinity of hydroxide materials, the more perfect octahedral symmetry and atomic ordering, resulting in the less exposed metal sites and limited electrocatalytic activity. Herein, a glassy state hydroxide material featuring with short-range order and long-range disorder structure is developed to achieve high intrinsic activity for OER. Specifically, a rapid freezing point precipitation method is utilized to fabricate amorphous multi-component hydroxide. Owing to the freezing-point crystallization environment and chaotic M-O (M = Ni/Fe/Co/Mn/Cr etc.) structures, the as-fabricated NiFeCoMnCr hydroxide exhibit a highly-disordered glassy structure, as-confirmed by X-ray/electron diffraction, enthalpic response, and pair distribution function analysis. The as-achieved glassy-state hydroxide materials display a low OER overpotential of 269 mV at 20 mA cm-2 with a small Tafel slope of 33.3 mV dec-1, outperform the benchmark noble-metal RuO2 catalyst (341 mV, 84.9 mV dec-1) . Operando Raman and density functional theory studies reveal that the glassy state hydroxide converted into disordered active oxyhydroxide phase with optimized oxygen intermediates adsorption under low OER overpotentials, thus boosting the intrinsic electrocatalytic activity.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

    求助全文

  • 文章类型: Journal Article
    在不同的处理条件下,通过一步氢氧化钾(KOH)活化将农业废物(Goji分支)热解为生物炭。首先对生物炭的结构特征和官能团进行了表征,然后以亚甲基蓝作为模型污染物对其吸附性能进行了评估。应用不同的吸附模型来拟合吸附过程并揭示可能的机理。发现吸附容量与生物炭的表面积密切相关(R2=0.9642),其中生物炭K50%W29%C-700(在50%KOH和29%水存在下在700°C下热解)具有最大的表面积(1378m2/g),并表现出最高的吸附能力(769mg/g)与其同源产品相比。生物炭K50%W29%C-700还显示出优异的可回收性和对其他常见有机污染物的有效吸附能力。结果表明,农业废物中的痕量水可以显着增强KOH参与的生产多孔生物炭的活化效率。
    The agricultural waste (Goji branch) was pyrolyzed into biochars with one-step potassium hydroxide (KOH) activation under different processing conditions. The biochars were first characterized in structural features and functional groups and then evaluated for adsorptive performance with methylene blue as a model pollutant. Different adsorption models were applied to fit the adsorption process and reveal the possible mechanisms. The adsorption capacity was found to strongly correlate (R2 = 0.9642) with the surface area of the biochars, among which biochar K50%W29%C-700 (pyrolysis at 700 °C in the presence of 50 % KOH and 29 % water) possessed the largest surface area (1378 m2/g) and exhibited the highest adsorption capacity (769 mg/g) compared to its homologous products. Biochar K50%W29%C-700 also showed excellent recyclability and potent adsorption capacity toward other common organic pollutants. The results suggest that traces of water in agricultural wastes could significantly intensify the KOH-involved activation efficiency of producing porous biochar.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

    求助全文

  • 文章类型: Journal Article
    为缓慢的析氧反应(OER)开发有效且负担得起的电催化剂仍然是通过水电解制氢的实际应用需要克服的重要障碍。将二氧化碳转化为增值化学品,和金属空气电池。最近,氢氧化物已显示出有望作为OER的电催化剂。原位或操作技术对于监测关键中间体以及了解反应过程尤其不可或缺。这对于揭示氢氧化物的形成/OER催化机理和制备具有成本效益的OER电催化剂极为重要。然而,缺乏对使用原位或操作技术研究这些机制的现状和挑战的全面讨论,这阻碍了我们识别和解决这一领域存在的障碍的能力。这篇综述概述了原位或操作技术,概述他们的能力,优势,和缺点。还详细讨论了通过原位或操作技术揭示的与氢氧化物的形成机理和OER催化机理有关的最新发现。此外,总结了该领域当前的一些挑战,并提供了适当的解决方案。
    Developing efficient and affordable electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a significant barrier that needs to be overcome for the practical applications of hydrogen production via water electrolysis, transforming CO2 to value-added chemicals, and metal-air batteries. Recently, hydroxides have shown promise as electrocatalysts for OER. In situ or operando techniques are particularly indispensable for monitoring the key intermediates together with understanding the reaction process, which is extremely important for revealing the formation/OER catalytic mechanism of hydroxides and preparing cost-effective electrocatalysts for OER. However, there is a lack of comprehensive discussion on the current status and challenges of studying these mechanisms using in situ or operando techniques, which hinders our ability to identify and address the obstacles present in this field. This review offers an overview of in situ or operando techniques, outlining their capabilities, advantages, and disadvantages. Recent findings related to the formation mechanism and OER catalytic mechanism of hydroxides revealed by in situ or operando techniques are also discussed in detail. Additionally, some current challenges in this field are concluded and appropriate solution strategies are provided.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

    求助全文

  • 文章类型: Journal Article
    开发快速且高活性的析氧反应(OER)催化剂以改变能量动力学技术对于制造清洁能源至关重要。在这里,我们通过原位重构策略制备了基于预催化剂MoS2/FeC2O4的三维(3D)中空Mo掺杂非晶态FeOOH(Mo-FeOOH)。Mo-FeOOH表现出良好的OER性能。具体来说,它具有285mV的过电位和在10mAcm-2时15h的耐久性。表征表明Mo包含在FeOOH晶格中,它不仅改变了FeOOH的电子能级,而且有效地提高了FeOOH对OER的固有活性。此外,原位拉曼分析表明,在整个OER过程中,FeC2O4逐渐转变为FeOOH活性位点。本研究为设计原位重构策略制备高电化学活性的杂原子掺杂催化剂提供了思路。
    Developing a fast and highly active oxygen evolution reaction (OER) catalyst to change energy kinetics technology is essential for making clean energy. Herein, we prepare three-dimensional (3D) hollow Mo-doped amorphous FeOOH (Mo-FeOOH) based on the precatalyst MoS2 /FeC2 O4 via in situ reconstruction strategy. Mo-FeOOH exhibits promising OER performance. Specifically, it has an overpotential of 285 mV and a durability of 15 h at 10 mA cm-2 . Characterizations indicate that Mo was included inside the FeOOH lattice, and it not only modifies the electronic energy levels of FeOOH but also effectively raises the inherent activity of FeOOH for OER. Additionally, in situ Raman analysis indicates that FeC2 O4 gradually transforms into the FeOOH active site throughout the OER process. This study provides ideas for designing in situ reconstruction strategies to prepare heteroatom doping catalysts for high electrochemical activity.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

    求助全文

  • 文章类型: Journal Article
    通常报道的煅烧策略通常需要高温才能使金属有机骨架(MOFs)颗粒开裂,这往往会导致纳米材料无法控制的生长。这里,第一次,我们利用电化学阴离子交换方法来控制MOFs的水解并合成多孔Ni/Co氢氧化物纳米片。电化学阴离子交换后,MOFs纳米片的有机配体可以回收再利用。在碱性溶液中向MOFs本体施加电场可以加速氢氧化物的成核速率并改变带电离子/分子的迁移行为。可以定制衍生物的微观结构,提高电极的深度充放电能力。因此,优化的Ni:Co摩尔比为7:3,电场施加时间为1000次循环[Ni0.7Co0.3(OH)2-1000c]的氢氧化物比没有电场辅助合成的材料具有更好的电化学性能:2115Cg-1(4230Fg-1)的高比电容。具有Ni0.7Co0.3(OH)2-1000c电极的混合超级电容器显示出74.7Whkg-1的高能量密度,提高了功率密度(5,990.6Wkg-1),和优异的循环稳定性(8,000个循环)。本研究不仅为低成本的制备提供了新的策略,用于超级电容器的深放电电极,但也提出了一种非常规的方法,用于将MOFs材料温和地合成为具有定制的微观形态的多孔纳米级衍生物。
    The commonly reported calcination strategy usually requires high temperature to crack the metal-organic frameworks (MOFs) particles, which often lead to uncontrollable growth of nanomaterials. Here, for the first time, we utilize an electrochemical anion-exchanged method to control the hydrolysis of MOFs and synthesize porous Ni/Co hydroxide nanosheets. After the electrochemical anion-exchange, the organic ligands of MOFs nanosheets can be recycled and reused. Applying an electric field to the MOFs bulk in alkaline solution can accelerate the nucleation rate of hydroxide and change the migration behavior of charged ions/molecules, which can tailor the microstructure of derivatives and improve deep charge and discharge capability of the electrodes. As a result, the hydroxide with the optimized Ni:Co molar ratio of 7:3 and electric-field application time of 1000 cycles [Ni0.7Co0.3(OH)2-1000c] provides much better electrochemical properties than the materials synthesized without electric-field assistance: a high specific capacitance of 2115C g-1 (4230F g-1). A hybrid supercapacitor with the Ni0.7Co0.3(OH)2-1000c electrode shows a high energy density of 74.7 Wh kg-1, an improved power density (5,990.6 W kg-1), and an excellent cyclic stability (8,000 cycles). This study not only provides a novel strategy for the preparation of low-cost, deep-discharge electrodes for supercapacitors, but also proposes an unconventional method for mild synthesizing MOFs materials into porous nanoscale derivatives with tailored micromorphology.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

       PDF(Sci-hub)

  • 文章类型: Journal Article
    尽管基于金属有机骨架(MOFs)的电极材料在电化学领域得到了广泛的研究,导电性差的起源仍然是制约其发展的瓶颈。在这里,我们通过在Fe-MOF表面生长一层氢氧化物来构建导电电路,复合材料(Fe-MOF@Ni(OH)2)应用于超级电容器领域,OER,和电化学传感。Fe-MOF@Ni(OH)2不仅保持了Fe-MOF的内在优势,而且还提高了导电性。Fe-MOF@Ni(OH)2在1Ag-1时表现出188mAhg-1的高比容量。非对称超级电容器(Fe-MOF@Ni(OH)2-20//AC)的能量密度达到67.1Whkg-1。在氧气析出反应过程中,材料的过电位在10mAcm-2时为280mV,Tafel斜率为37.6mVdec-1。电化学传感测试表明,BPA的检测极限为5μM。因此,这些结果为多功能电极材料的设计提供了关键见解。
    Although electrode materials based on metal organic frameworks (MOFs) were widely studied in the electrochemistry field, the origin of poor conductivity is still a bottleneck restricting their development. Herein, we constructed a conductive circuit by growing a layer of hydroxide on the surface of the Fe-MOF, and composite materials (Fe-MOF@Ni(OH)2) are applied in the fields of supercapacitor, OER, and electrochemical sensing. Fe-MOF@Ni(OH)2 not only maintains the intrinsic advantages of Fe-MOF, but also improves the electrical conductivity. Fe-MOF@Ni(OH)2 exhibits a high specific capacity of 188 mAh g-1 at 1 A g-1 . The energy density of the asymmetric supercapacitor (Fe-MOF@Ni(OH)2-20//AC) reaches 67.1 Wh kg-1. During the oxygen evolution reaction, the overpotential of the material is 280 mV at 10 mA cm-2, and the Tafel slope is 37.6 mV dec-1. The electrochemical sensing tests showed the detection limit of BPA is 5 μM. Hence, these results provide key insights into the design of multifunctional electrode materials.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

       PDF(Sci-hub)

  • 文章类型: Journal Article
    The unsatisfactory cycle life of nickel-based cathodes hinders the widespread commercial usage of nickel-zinc (Ni-Zn) batteries. The most frequently used methods to improve the cycle life of Ni-based cathodes are usually complicated and/or involve using organic solvents and high energy consumption. A facile process based on the hydrolysis-induced exchange of the cobalt-based metal-organic framework (Co-MOF) was developed to prepare aluminum (Al)-doped cobalt-nickel double hydroxides (Al-CoNiDH) on a carbon cloth (CC). The entire synthesis process is highly efficient, energy-saving, and has a low negative impact on the environment. Compared to undoped cobalt-nickel double hydroxide (Al-CoNiDH-0%), the as-prepared Al-CoNiDH as the electrode material displays a remarkably improved cycling stability because the Al-doping successfully depresses the transition in the crystal phase and microstructure during the long cycling. Benefiting from the improved performance of the optimal Al-CoNiDH electrode (Al-CoNiDH-5% electrode), the as-constructed aqueous Ni-Zn battery with Al-CoNiDH-5% as the cathode (Al-CoNiDH-5%//Zn) displays more than 14% improvement in the cycle life relative to the Al-CoNiDH-0%//Zn battery. Moreover, this Al-CoNiDH-5%//Zn battery achieves a high specific capacity (264 mAh g-1), good rate capability (72.4% retention at a 30-fold higher current), high electrochemical energy conversion efficiency, superior fast-charging ability, and strong capability of reversible switching between fast charging and slow charging. Furthermore, the as-assembled quasi-solid-state Al-CoNiDH-5%//Zn battery exhibits a decent electrochemical performance and satisfactory flexibility.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

       PDF(Sci-hub)

  • 文章类型: Journal Article
    Influences and mechanisms of chemically synthesized nano-C-S-H gel addition on fresh properties of the cement-based materials with sucrose as a retarder were investigated in this study. The results showed that the flow value of the fresh cement paste was gradually but slightly reduced with increasing nano-C-S-H gel addition due to its fibrous but well-dispersed characteristic in both water and cement paste. The semi-adiabatic calorimetry testing results verified that incorporation of nano-C-S-H gel could greatly mitigate the retarding effect of sucrose on cement hydration. The total organic carbon (TOC) indicated that the addition of the nano-C-S-H gel helps to reduce adsorption of the sucrose molecules into the protective layer, thus the semi-permeability of the protective layer was less reduced and that is why the addition of the nano-C-S-H gel can mitigate the retardation caused by the sucrose. Through XRD analysis, it was found that the CH crystals are more prone to grow along the (0001) plane with larger size in the paste with nano-C-S-H addition before the induction period starts, because the C-S-H nanoparticles can form 3D network to slow down the diffusion rate of the released ions and eliminate the convection in the paste, thus suppress the 3D nucleation and growth of the CH crystals. The XRD analysis also indicated a refinement of the ettringite crystals in the paste with sucrose addition, but introduction of nano-C-S-H gel did not show further refinement, which was also verified by the SEM observation.
    导出

    更多引用

    收藏

    翻译标题摘要

    我要上传

       PDF(Sci-hub)

       PDF(Pubmed)

公众号