Solar‐driven upgrading of biomass‐derived 5‐hydroxylmethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) holds great promise for sustainable production of bio‐plastics and resins. However, the process is limited by poor selectivity and sluggish kinetics due to the vertical coordination of HMF at relatively strong metal sites. Here, we purposely developed a Cu(II) porphyrin framework featuring side‐chain incorporated urea linkages, denoted as TBUPP‐Cu MOF, to render HMF a weak hydrogen bond at the urea site and flat adsorption via π–π stacking with the benzyl moiety. The unique configuration promotes the approaching of –CHO of HMF to the photoexcited porphyrin ring towards kinetically and thermodynamically favourable intermediate formation and subsequent desorption. The charge localization and orbital energy alignment enable the selective activation of O2 over the porphyrin to generate ·O2− and 1O2 instead of highly oxidative H2O2 and ·OH via spin‐flip electron transfer, which drive the ambient oxidation of proximal –CHO. The effective utilisation of redox species and circumvented over‐oxidation facilitate a FDCA selectivity of >90% with a high turnover number of 193 molHMF molCu−1. The facile purification of high‐purity FDCA and zero‐waste recycling of intermediates and durable catalyst feature TBUPP‐Cu MOF a promising photo‐oxidation platform towards net‐zero biorefining and organic transformations.

中文翻译：

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尿素结合铜（II）卟啉框架上生物质呋喃的氢键增强光重整

太阳能驱动的生物质衍生的 5-羟甲基糠醛 (HMF) 升级为 2,5-呋喃二甲酸 (FDCA) 为生物塑料和树脂的可持续生产带来了巨大的希望。然而，由于 HMF 在相对较强的金属位点上的垂直配位，该过程受到选择性差和动力学缓慢的限制。在这里，我们特意开发了一种具有侧链掺入脲键的 Cu(II) 卟啉框架，表示为 TBUPP-Cu MOF，使 HMF 在脲位点形成弱氢键，并通过与苄基部分的 π-π 堆积实现平坦吸附。独特的构型促进了 HMF 的 –CHO 接近光激发的卟啉环，从而形成动力学和热力学有利的中间体并随后解吸。电荷定位和轨道能量排列使得 O2 在卟啉上选择性激活，通过自旋翻转电子转移生成·O2− 和 1O2，而不是高度氧化性的 H2O2 和·OH，从而驱动近端 –CHO 的环境氧化。氧化还原物质的有效利用和避免的过度氧化促进了 FDCA 选择性 >90%，周转数高达 193 molHMF molCu−1。高纯度 FDCA 的轻松纯化以及中间体和耐用催化剂的零废物回收使得 TBUPP-Cu MOF 成为实现净零生物精炼和有机转化的有前途的光氧化平台。