Shahin Rehana, Yadav Rajesh K, Verma Rajesh K, Mishra Shaifali, Singh Chandani, Baeg Jin-OoK
Department of Chemistry and Environmental Science, Madan Mohan Malaviya University of Technology, Gorakhpur, India.
Department of Mechanical Engineering, Harcourt Butler Technical University, Kanpur, India.
Photochem Photobiol. 2025 Jul 2. doi: 10.1111/php.70007.
Photocatalytic CO₂ fixation into solar fuels offers a promising route for renewable energy storage by converting CO₂ into chemical bonds. Among various products, formic acid is considered the most reliable candidate for industrial applications due to its high efficiency and sustainable feasibility. Various catalysts, including metals, chalcogenides, transition metals, and carbon-based materials, have been explored for this purpose. Polymeric organic frameworks are a class of crystalline polymers with tunable structures, making them potential candidates for metal-free photocatalysts. However, their low crystallinity often limits light-harvesting efficiency and photocatalytic activity, posing a challenge for industrial applications. The primary obstacles in this field are low activity and poor selectivity of photocatalysts. In this study, we propose a soft-template induction strategy to construct a metal-free heterojunction polymeric framework based on 5,15-di-(4-aminophenyl)-10,20-diphenyl porphyrin (BP) and perylene tetra-anhydride (PT), referred to as PTBP. This polymer exhibits high crystallinity and strong solar light absorption. The PTBP framework demonstrates better performance in solar-powered molecular artificial photosynthesis, achieving significant improvements over PT. Specifically, PTBP exhibits high 1,4-NADH/NADPH regeneration efficiencies (52.51%/58.41%) compared to PT (9.11%/10.1%), a substantial NADH consumption (119.25 μmol) in exclusive solar fuel production from CO₂ within 1 h, and excellent yield (50.37%) in the photocatalytic conversion of dopamine into an indole-derivative, surpassing PT (13.93%). The current finding highlights the benchmark photocatalytic potential of the PTBP polymeric framework's capacity for photocatalysis for CO fixation and conversion of dopamine into indole derivatives.
通过将二氧化碳转化为化学键，光催化二氧化碳固定为太阳能燃料为可再生能源存储提供了一条有前景的途径。在各种产物中，甲酸因其高效率和可持续可行性而被认为是工业应用中最可靠的候选物。为此，人们探索了各种催化剂，包括金属、硫族化物、过渡金属和碳基材料。聚合物有机框架是一类结构可调的结晶聚合物，使其成为无金属光催化剂的潜在候选物。然而，它们的低结晶度常常限制光捕获效率和光催化活性，给工业应用带来挑战。该领域的主要障碍是光催化剂的低活性和差选择性。在本研究中，我们提出了一种软模板诱导策略，以构建基于5,15-二-(4-氨基苯基)-10,20-二苯基卟啉（BP）和苝四酸二酐（PT）的无金属异质结聚合物框架，称为PTBP。这种聚合物表现出高结晶度和强烈的太阳光吸收。PTBP框架在太阳能驱动的分子人工光合作用中表现出更好的性能，比PT有显著改进。具体而言，与PT（9.11%/10.1%）相比，PTBP表现出高的1,4-NADH/NADPH再生效率（52.51%/58.41%），在1小时内由二氧化碳独家生产太阳能燃料时大量的NADH消耗（119.25μmol），以及在多巴胺光催化转化为吲哚衍生物中的优异产率（50.37%），超过PT（13.93%）。当前的发现突出了PTBP聚合物框架在光催化固定二氧化碳和将多巴胺转化为吲哚衍生物方面的基准光催化潜力。
