Polyoxometalated metal-organic framework superstructure for stable water oxidation

Stable non-precious catalysts are vital for large-scale alkaline water electrolysis. Here, we report a grafted superstructure, MOF@POM, formed by self-assembling a metal-organic framework (MOF) with polyoxometalate (POM). In situ electrochemical transformation converts MOF into active metal (oxy)hydroxides with a low overpotential of 178 millivolts at 10 milliamperes per square centimeter. An anion exchange membrane water electrolyzer incorporating this catalyst achieves 3 amperes per square centimeter at 1.78 volts at 80 degrees Celsius and stable operation at 2 amperes per square centimeter for 5,140 hours at room temperature. In-situ electrochemical spectroscopy and theoretical studies revealed that the synergistic interactions between metal atoms create a fast electron-transfer channel from catalytic iron and cobalt sites, nickel, and tungsten in the polyoxometalate to the electrode, stabilizing the metal sites and preventing dissolution., , , # Data from: Polyoxometalated metal-organic framework superstructure for stable water oxidation Dataset DOI: [10.5061/dryad.hqbzkh1t9](10.5061/dryad.hqbzkh1t9) ## Description of the data and file structure Dataset 1 is the data from Figure 1E: Full-range synchrotron PDF analysis for MOF@POM, with the corresponding Rietveld refinement and the calculated partial PDF patterns of the Ni-Fe distance.This dataset contains the full-range synchrotron PDF analysis of MOF@POM, along with the corresponding Rietveld refinement results and partial PDF patterns from which the Ni–Fe distance was derived. The first three columns (x1, y1, y2) represent the experimental measurements and the fitting results. The fourth and fifth columns (x2, y3) provide the p-PDF data for Ni–Fe. The final two columns (x3, y4) show the residuals between y1 and y2. Both the x- and y-axes are given in units of atomic distance. Dataset 2 is the data from Figure 2A: CV curves of MOF, MOF@POM, and the reference samples.In t...,稳定的非贵金属催化剂对于规模化碱性水电解而言至关重要。本研究报道了一种接枝型超结构MOF@POM，通过将金属有机框架（metal-organic framework, MOF）与多金属氧酸盐（polyoxometalate, POM）自组装制备得到。经原位电化学转化后，该结构中的MOF被转化为活性金属（氧）氢氧化物，在10毫安每平方厘米的电流密度下过电位仅为178毫伏。搭载该催化剂的阴离子交换膜水电解槽在80℃条件下可实现1.78 V电压下3安培每平方厘米的电流密度，并可在室温下以2安培每平方厘米的电流稳定运行5140小时。通过原位电化学光谱与理论计算研究发现，金属原子间的协同相互作用构建了快速电子传输通道，使催化活性的铁、钴位点以及多金属氧酸盐中的镍、钨位点能够高效向电极传输电子，从而稳定金属位点并抑制其溶解。 # 数据来源：用于稳定水氧化的多金属氧酸化金属有机框架超结构 数据集DOI：10.5061/dryad.hqbzkh1t9 ## 数据与文件结构说明 数据集1对应图1E：MOF@POM的全范围同步辐射对分布函数（PDF）分析数据，包含对应的里特维尔德（Rietveld）精修结果以及Ni-Fe距离的计算局部PDF图谱。该数据集涵盖MOF@POM的全范围同步辐射PDF分析数据、配套的Rietveld精修结果，以及用于提取Ni-Fe距离的局部PDF图谱。其中前3列（x1、y1、y2）分别代表实验测量值与拟合结果；第4、5列（x2、y3）提供了Ni-Fe的局部对分布函数（p-PDF）数据；最后2列（x3、y4）展示了y1与y2之间的残差。所有坐标轴的单位均为原子间距。 数据集2对应图2A：MOF、MOF@POM及参比样品的循环伏安（CV）曲线数据。在 t...,