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Metal center regulation of the porphyrin unit in covalent organic polymers for boosting the photocatalytic CO2 reduction activity
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机译：Metal center regulation of the porphyrin unit in covalent organic polymers for boosting the photocatalytic CO2 reduction activity
Mimicking plant photosynthesis for converting CO2 into high-energy chemical fuels on photocatalysts powered by sunlight is expected to simultaneously alleviate the current energy shortage and global warming. Among the various photocatalysts developed for solar energy conversion, covalent organic polymers (COPs) have attracted increasing attention because of their predictable synthetic routes, variable electronic structures, and precisely regulated active sites. Here, a series of amido-coupled metal porphyrin (MPor)–Ru(ii) pincer complexes (RuN3) COPs (MPor–RuN3, M = Co, Ni, Cu or Zn) were synthesized and adopted as photocatalysts for the CO2 reduction reaction (CO2RR). It was found that the metal center regulation of the porphyrin unit in COPs can effectively boost the photocatalytic CO2RR activity with CO yield following an order of CuPor–RuN3 > NiPor–RuN3 > ZnPor–RuN3 > CoPor–RuN3 with the aid of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as a sacrificial electron donor. Especially, CuPor–RuN3 COP delivered the highest CO yield under both visible light (74.3 μmol h−1 g−1) and full spectrum (143.7 μmol h−1 g−1) illumination of Xe-lamp, 4.7 and 4.4 times that of the metal-free control (H2Por–RuN3), respectively. The control experiments and theoretic calculations revealed that the metal center of the porphyrin unit not only affects the photoexcited charge separation but also influences the BIH oxidation dynamics on the porphyrin units, which has rarely been discussed before. Both of them then jointly contributed to the significantly improved CO2RR activity of the CuPor–RuN3 COP. This work shows an effective method to boost the CO2RR performance of porphyrin-based COPs by regulating the structure and composition, and provides valuable insights into the photocatalytic mechanism at the molecular level.
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机译：模拟植物的光合作用将二氧化碳在论文的高能化学燃料同时由阳光预计缓解当前能源短缺和全球变暖。开发太阳能转换、共价有机聚合物(警察)吸引了越来越多关注,因为它们可预测的合成路线,可变电子结构,精确调节活跃的网站。amido-coupled金属卟啉(MPor)俄文(2)螯复合物(RuN3)警察(MPor-RuN3 M =有限公司镍、铜、锌)是合成和作为二氧化碳还原反应催化剂(CO2RR)。监管卟啉单元的警察有效地提高光催化CO2RR活动与公司产生订单后的帮助下
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