Liu Xiao-Cheng, Wu Geng, Han Xiao, Wang Yang, Wu Bei, Wang Gongming, Mu Yang, Hong Xun
Hefei National Laboratory for Physical Sciences at the Microscale, Department of Applied Chemistry, Department of Environmental Science and Engineering, Center of Advanced Nanocatalysis (CAN), University of Science & Technology of China, Hefei, Anhui, 230026, P. R. China.
Adv Mater. 2025 Feb;37(7):e2416749. doi: 10.1002/adma.202416749. Epub 2025 Jan 2.
Substitution metal doping strategies are crucial for developing catalysts capable of activating O, but the leaching of metal dopants has greatly hindered their potential for extensive oxidation reactions under mild conditions. Here, the study develops an entropy-increase strategy to synthesize high-entropy metal (Mg, Ca, Mn, Fe, and Co) interstitial functionalized anatase TiO (HE-TiO) nanosheets, demonstrating remarkable degradation efficiency across a wide pH range and exceptional stability in a flow-by electro-catalytic reactor. Relative to that of pristine TiO, the intense lattice distortion on the (001) plane, an average lattice expansion of 2% on the (100) plane, and decrease of second shell peak of X-ray absorption spectra serve as compelling evidence for the formation of metal interstitials in HE-TiO. Theoretical analysis and in situ synchrotron radiation Fourier transform infrared studies reveal that the electron of metal interstitials can populate the subgap states within the host TiO, enabling a moderate adsorption band for robust and efficient O activation. This study introduces a universal strategy for synthesizing a novel class of high-entropy materials with integrated metal interstitials in metal oxides, promising to enhance the stability and efficiency of O activation catalysts and broaden their potential applications.
替代金属掺杂策略对于开发能够激活O的催化剂至关重要，但金属掺杂剂的浸出极大地阻碍了它们在温和条件下进行广泛氧化反应的潜力。在此，该研究开发了一种熵增策略来合成高熵金属（Mg、Ca、Mn、Fe和Co）间隙功能化的锐钛矿TiO（HE-TiO）纳米片，其在宽pH范围内表现出显著的降解效率，并且在流动式电催化反应器中具有出色的稳定性。相对于原始TiO，（001）面上强烈的晶格畸变、（100）面上平均2%的晶格膨胀以及X射线吸收光谱第二壳层峰的降低，是HE-TiO中形成金属间隙的有力证据。理论分析和原位同步辐射傅里叶变换红外研究表明，金属间隙的电子可以填充主体TiO内的亚带隙态，从而为稳健且高效的O激活提供适度的吸附带。这项研究引入了一种通用策略，用于合成一类新型的在金属氧化物中具有集成金属间隙的高熵材料，有望提高O激活催化剂的稳定性和效率，并拓宽其潜在应用。
