He Tiwei, Tang Hongchao, Wu Jie, Wang Jiaxuan, Zhang Mengling, Lu Cheng, Huang Hui, Zhong Jun, Cheng Tao, Liu Yang, Kang Zhenhui
Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, 199 Ren'ai Road, Suzhou, 215123, Jiangsu, China.
Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint Research Center for Advanced Functional Materials, Macau University of Science and Technology, Taipa, 999078, Macao, China.
Nat Commun. 2024 Sep 7;15(1):7833. doi: 10.1038/s41467-024-52162-3.
Carbon-based metal-free catalysts are promising green catalysts for photocatalysis and electrocatalysis due to their low cost and environmental friendliness. A key challenge in utilizing these catalysts is identifying their active sites, given their poor crystallinity and complex structures. Here we demonstrate the key structure of the double-bonded conjugated carbon group as a metal-free active site, enabling efficient O photoreduction to HO through a cascaded water oxidation - O reduction process. Using ethylenediaminetetraacetic acid as a precursor, we synthesized various carbon-based photocatalysts and analyzed their structural evolution. Under the polymerization conditions of 260 °C to 400 °C, an N-ethyl-2-piperazinone-like structure was formed on the surface of the catalyst, resulting in high photocatalytic HO photoproduction (2884.7 μmol gh) under visible light. A series of control experiments and theoretical calculations further confirm that the double-bond conjugated carbonyl structure is the key and universal feature of the active site of metal-free photocatalysts.
碳基金属无催化剂因其低成本和环境友好性，是用于光催化和电催化的有前景的绿色催化剂。鉴于其结晶度差和结构复杂，利用这些催化剂的一个关键挑战是确定其活性位点。在此，我们证明了双键共轭碳基团的关键结构作为无金属活性位点，通过级联水氧化-氧还原过程实现高效的氧光还原为过氧化氢。使用乙二胺四乙酸作为前驱体，我们合成了各种碳基光催化剂并分析了它们的结构演变。在260°C至400°C的聚合条件下，催化剂表面形成了类似N-乙基-2-哌嗪酮的结构，在可见光下产生高光催化过氧化氢产量（2884.7 μmol g⁻¹ h⁻¹）。一系列对照实验和理论计算进一步证实，双键共轭羰基结构是无金属光催化剂活性位点的关键和普遍特征。
