Zhang Wenjing, Hao Xuewei, Liu Xinlin, Chu Mingyu, Li Shengming, Wang Xuchun, Jiang Feng, Wang Lu, Zhang Qiao, Chen Jinxing, Wang Dingsheng, Cao Muhan
Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, Soochow University, Suzhou, 215123, People's Republic of China.
X-ray Science Division, Argonne National Laboratory, Lemont, Illinois, 60439, United States.
Angew Chem Int Ed Engl. 2025 Apr 25;64(18):e202500814. doi: 10.1002/anie.202500814. Epub 2025 Feb 28.
Photoreforming presents a promising strategy for upcycling waste polyester-derived alcohol into valuable chemicals. However, it remains a great challenge due to its low performance and unsatisfactory selectivity toward high-value C products. Here, we report the highly efficient and selective conversion of ethylene glycol (EG, a monomer of polyethylene terephthalate (PET)) to glycolaldehyde using atomically dispersed Pd species supported on TiO catalyst. A glycolaldehyde production rate of 5072 μmol g h with a selectivity of 90.0 % and long-term durability can be achieved. Experimental and theoretical results show that Pd single atoms can enhance the photocatalytic activity by enriching the photogenerated holes, which are the dominant species for the selective oxidation of EG to glycolaldehyde. More importantly, the adsorption of EG molecules on the catalysts is significantly promoted, which is subsequently transformed into RO⋅ radicals, a crucial intermediate in producing glycolaldehyde. Additionally, Pd single atoms on TiO enable the reduction of the glycolaldehyde desorption barrier, thereby facilitating high selectivity and inhibiting further oxidation to C products. This work provides new insights into the photocatalytic conversion of polyester wastes by atomic engineering.
光重整为将废弃聚酯衍生的醇升级转化为有价值的化学品提供了一种很有前景的策略。然而,由于其性能较低且对高价值碳产物的选择性不理想,它仍然是一个巨大的挑战。在此,我们报道了使用负载在TiO催化剂上的原子分散的钯物种将乙二醇(EG,聚对苯二甲酸乙二酯(PET)的单体)高效且选择性地转化为乙醇醛。可以实现5072 μmol g h的乙醇醛产率,选择性为90.0%,并且具有长期耐久性。实验和理论结果表明,钯单原子可以通过富集光生空穴来提高光催化活性,而光生空穴是将EG选择性氧化为乙醇醛的主要物种。更重要的是,EG分子在催化剂上的吸附显著增强,随后转化为RO⋅自由基,这是生成乙醇醛的关键中间体。此外,TiO上的钯单原子能够降低乙醇醛的解吸势垒,从而有利于高选择性并抑制进一步氧化为碳产物。这项工作通过原子工程为聚酯废料的光催化转化提供了新的见解。