标题： 使用具有畸变原子尺度结构的高熵氧氮化物将塑料废物光重整为有价值的产品和氢气 显示英文标题

标题： Photoreforming of plastic waste into valuable products and hydrogen using a high-entropy oxynitride with distorted atomic-scale structure

摘要： 塑料废物的持续存在对环境造成了严重的问题，直接或间接地影响了生物和人类的健康。 光重整是一种环保的方法，它仅利用太阳能将塑料废物转化为绿色氢气（H₂）和有价值的有机产物。 本研究显示，通过向含Ti-Zr-Hf-Nb-Ta的高熵氧化物（HEO）中添加氮合成的高熵氧氮化物（HEON）光催化剂，在聚对苯二甲酸乙二醇酯（PET）光重整中产生氢气、甲酸和醋酸的潜力高于相应的HEO。 同步辐射X射线吸收近边结构（XANES）和扩展X射线吸收精细结构（EXAFS）研究表明，除了氧和氮的轨道杂化外，氮原子还扭曲了结构，并完全改变了铌和钛（导带的主要贡献者）周围的环境，扩大了锆和钽的原子键，缩小了铪的原子键，并降低了钛、铌和钽的结合能。 这些电子结构的变化导致了更窄的带隙和减少的电子-空穴复合，从而提高了光重整性能。 本研究引入了具有扭曲原子键结构的HEON，作为通过光催化将塑料转化为高价值有机化学品和H₂的有效低带隙且稳定的催化剂。 显示英文摘要

摘要： The persistent existence of plastic waste causes serious problems for the environment, directly and indirectly affecting the health of organisms and humans. Photoreforming is a nature-friendly method that only uses solar energy to convert plastic waste into green hydrogen (H2) and valuable organic products. This study shows that a high-entropy oxynitride (HEON) photocatalyst, synthesized by the addition of nitrogen to a Ti-Zr-Hf-Nb-Ta-containing high-entropy oxide (HEO), exhibits a higher potential for the production of H2, formic acid and acetic acid from polyethylene terephthalate (PET) photoreforming compared to the relevant HEO. Examination of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) by synchrotron light shows that, in addition to hybridization of 2p orbitals from oxygen and nitrogen, nitrogen atoms distort the structure and completely change the neighborhood of niobium and titanium (a main contributor to the conduction band), expands the atomic bonds of zirconium and tantalum, contracts the atomic bonds of hafnium and decreases the binding energy of titanium, niobium and tantalum. These electronic structure changes lead to a narrower bandgap and diminished electron-hole recombination, enhancing the photoreforming performance. This study introduces HEONs with distorted atomic bond structures as efficient low-bandgap and stable catalysts for transforming plastics into high-value organic chemicals and H2 by photocatalysis.