Bionic Mineralization toward Scalable MOF Films for Ampere-Level Biomass Upgrading

With significant advances in metal-organic framework (MOF) nanostructure preparation, however, the facile synthesis of large-scale MOF films with precise control of the interface structure and surface chemistry is still challenging to achieve with satisfactory performance. Herein, we introduce a universal strategy bridging metal corrosion chemistry and bionic mineralization to synthesize 16 MOF films on 7 metal supports under ambient conditions. The robustness to explore unlimited libraries of MOF films (e.g., carboxylate-, N-heterocycle-, phenolic-, and phosphonate-MOFs) on supports is evoked by independently regulating the metal redox behavior, electrolyte properties, and organic ligands along with hydrogen evolution or oxygen reduction, which offers the basic guidelines for regulating the microstructure and composition of MOFs on the Pourbaix diagram. In conjunction with multiple manufacturing methods, we demonstrated proof of concept for "printing" a large variety of MOF patterns from micrometer to meter scales. Furthermore, a large-area electrolyzer (64 cm²) devised enables 5-hydroxymethylfurfural oxidation to achieve a record-breaking current of 3.0 A at 1.63 V with 2,5-furandicarboxylic acid production, leading to the simultaneous production of H₂ gas and valuable feedstocks. The improved electrocatalytic activity for significantly boosting the 5-hydroxymethylfurfural oxidation exemplifies one of the functional MOF films for given applications beyond biomass upgrading.