Constructing Hierarchical Metal–Organic Framework/Poly(m-phenylenediamine) Composites with Nanosheet Arrays via Phase Transition for Photothermal Catalysis

Considering the abundance and pollution-free nature of solar energy, it is necessary to design photothermal catalysts to obtain high-value chemicals driven by the endothermic catalytic reaction. Herein, PC-1/PmPD and PC-2/PmPD with hierarchical nanostructure assembled from nanosheet arrays are fabricated by phase transition from metastable precursor metal–organic frameworks (MOFs) under the stimulation of methanol and m-phenylenediamine (mPD). This phase transition involves dissolution-recrystallization and polymerization in one step, which not only completes precise morphology transformation but also attaches functional polymer in the composites. Owing to the photothermal effect and catalytic activity provided by the poly(m-phenylenediamine) (PmPD) and hierarchical nanostructures, such as abundant optical traps and more exposed active sites on the outer surface, PC-1/PmPD and PC-2/PmPD achieve efficient photothermal catalytic activity in the cycloaddition reaction of carbon dioxide driven by simulated sunlight at room temperature. The construction of hierarchical MOFs/polymer composites with nanosheet arrays as photothermal catalysts may open opportunities to expand their diversity and range of potential applications.