Tuning Interaction and Diffusion for Dimethyl Disulfide Adsorption on Cu-BTC Frameworks via Low Transition-Metal Doping

Abstract

Metal–organic frameworks (MOFs) have been finding increasing involvements in the capture of environmentally unfriendly compounds including volatile organosulfides contained in a wide range of energy sources owing to their editable structures. In this study, modulation of interaction and diffusion for sulfide adsorption on Cu-BTC frameworks was achieved via doping a series of transition-metal ions (Ni, Co, Fe, Zn, and Cr) at a low content through post-synthesis in an ethanol system. Synthesized samples were characterized, and dimethyl disulfide (DMDS) adsorption on different metal-doped structures were carefully studied through adsorption measurements combined with computational simulation. The results indicate that the transition-metal doping into the Cu-BTC structure at low content not only enhances the guest–host interaction via altering the cation compositions (introducing external ions along with reduction of Cu­(II) to Cu­(I)) but also promotes pore diffusion of DMDS through modifying porosities of the porous architectures. The present study highlights the tunable modification of the metal–organic framework structures via low metal doping and provides insights into the function-oriented structural optimization of their infrastructures.

Introducing of Cu(I) in MOFs by In Situ Reduction with Ni as the Catalyst for Efficient Olefin/Paraffin Separation

“…The adsorption capacities of 1-hexene and n -hexane were 152.7and 15.7 mg/g, with the highest 1-hexene/ n -hexane selectivity being 9.74. Zhu et al used a solvothermal approach to optimize the synthesis of Cu-BTC and discovered that its adsorption capabilities for 1-hexene and n -hexane were 122.31 and 18.95 mg/g, respectively, with a selectivity of 6.45. Furthermore, when the sample was modified by acetic acid, the adsorption amount of 1-hexene increased to 187.90 mg/g, while that of n -hexane decreased from 18.95 to 10.75 mg/g, resulting in an improvement in selectivity from 6.45 to 17.48.…”

“…Furthermore, when the sample was modified by acetic acid, the adsorption amount of 1-hexene increased to 187.90 mg/g, while that of n-hexane decreased from 18.95 to 10.75 mg/g, resulting in an improvement in selectivity from 6.45 to 17.48. Qian et al 29 discovered that the ethanol/ transition metal system may convert some Cu(II) in Cu-BTC to Cu(I) while altering the pore shape to improve the adsorption performance of dimethyl disulfide (DMDS).…”

Post-synthesis modification of metal–organic frameworks: synthesis, characteristics, and applications

“…192 The interaction energy calculation results showed that all the metal-doped MOFs had more exothermic energies for interacting with DMDS than the original Cu-BTC, indicating stronger host-guest interactions within the modied MOFs. 192 Additionally, computational simulation results demonstrated that the captured DMDS molecules were positioned near the doped metal ions (Fig. 21), which was consistent with the batch adsorption experiment results.…”

“…A series of metal-doped (Co, Fe, Zn, Cr, Ni) Cu-BTCs were developed by PSM for dimethyl disulfide (DMDS) adsorption. 192 Computational simulation was used to elucidate the effect of metal doping on the DMDS affinity of the modified MOFs. 192 The interaction energy calculation results showed that all the metal-doped MOFs had more exothermic energies for interacting with DMDS than the original Cu-BTC, indicating stronger host–guest interactions within the modified MOFs.…”

“…192 Computational simulation was used to elucidate the effect of metal doping on the DMDS affinity of the modified MOFs. 192 The interaction energy calculation results showed that all the metal-doped MOFs had more exothermic energies for interacting with DMDS than the original Cu-BTC, indicating stronger host–guest interactions within the modified MOFs. 192 Additionally, computational simulation results demonstrated that the captured DMDS molecules were positioned near the doped metal ions (Fig.…”