Silver-Nanoparticle-Assisted Modulation of NH₃ Desorption on MIL-101

Ammonia has recently emerged as a promising hydrogen carrier for renewable energy conversion. Establishing a better understanding and control of ammonia adsorption and desorption is necessary to improve future energy generation. Metal-organic frameworks (MOFs) have shown improved ammonia capacity and stability over conventional adsorbents such as silica and zeolite. However, ammonia desorption requires high temperature over 150 °C, which is not desirable for energy-efficient ammonia reuse and recycling. Here, we loaded silver nanoparticles from 6.6 to 51.4 wt% in MIL-101 (Ag@MIL-101) using an impregnation method to develop an efficient MOF-based hybrid adsorbent for ammonia uptake. The incorporation of metal nanoparticles into MIL-101 has not been widely explored for ammonia uptake, even though such hybrid nanostructures have significantly enhanced catalytic activities and gas sensing capacities. Structural features of Ag@MIL-101 with different Ag wt% were examined using transmission electron microscopy, X-ray powder diffraction, and infrared spectroscopy, demonstrating successful formation of silver nanoparticles in MIL-101. Ag@MIL-101 (6.6 wt%) showed hysteresis in the N₂ isotherm and an increase in the fraction of larger pores, indicating that mesopores were generated during the impregnation. Temperature-programmed desorption with ammonia was performed to understand the binding affinity of ammonia molecules on Ag@MIL-101. The binding affinity was the lowest with Ag@MIL-101 (6.6 wt%), including the largest relative fraction in the amount of desorbed ammonia molecules. It was presumed that cooperative interaction between the silver nanoparticle and the MIL-101 framework for ammonia molecules could allow such a decrease in the desorption temperature. Our design strategy with metal nanoparticles incorporated into MOFs would contribute to develop hybrid MOFs that reduce energy consumption when reusing ammonia from storage.