Efficient hydrogen production via NaBH4 methanolysis enhanced by bismuth terephthalic acid metal–organic framework

The bismuth terephthalate metal–organic framework (Bi(TPA).MOF) was synthesized as a methanolysis catalyst using a solvothermal method, by reacting terephthalic acid (TPA) with bismuth nitrate pentahydrate (Bi(NO₃)₃·5H₂O) in dimethylformamide (DMF) at 383.15 K. The structure, morphology, and composition of the resulting MOF were characterized using advanced surface analytical techniques, including X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, and scanning electron microscopy coupled with energy-dispersive X-ray (SEM–EDX), which confirmed successful formation of the Bi(TPA).MOF structure. The catalytic performance of Bi(TPA).MOF was then assessed in the sodium borohydride (NaBH₄) methanolysis reaction, demonstrating remarkable activity. The optimization of key reaction parameters, such as catalyst loading, NaBH₄ concentration, methanol volume, and reaction temperature, was conducted. Notably, Bi(TPA).MOF exhibited an outstanding hydrogen generation rate (HGR) of 321,996 mL/min·g_catalyst, with an activation energy of 39.9 kJ/mol, calculated via the Arrhenius equation. These results significantly surpass those previously reported in the literature, positioning Bi(TPA).MOF as a promising and efficient catalyst for enhancing hydrogen production through NaBH₄ methanolysis.