High Ammonia Adsorption in MFM-300 Materials: Dynamics and Charge Transfer in Host–Guest Binding

• DOI: 10.1021/jacs.0c11930
• Publication Date: 2021-02-20T11:52:27Z
• Authors: Xue Han; Wanpeng Lu; Yinlin Chen; Ivan da Silva; Jiangnan Li; Longfei Lin; Weiyao Li; Alena M. Sheveleva; Harry G. W. Godfrey; Zhenzhong Lu; Floriana Tuna; Eric J. L. McInnes; Yongqiang Cheng; Luke L. Daemen; Laura J. McCormic...; Simon J. Teat; Mark D. Frogley; Svemir Rudić; Pascal Manuel; Anibal J. Ramirez...; Sihai Yang; Martin Schröder
• Keywords: Chemical Sciences not elsewhere classified; mmol; Plant Biology; 02 engineering and technology; Biochemistry; Microbiology; DFT; 530; 01 natural sciences; V III; MFM; Macromolecular and Materials Chemistry; N 2 H 4; Inorganic Chemistry; Engineering; Affordable and Clean Energy; Environmental Sciences not elsewhere classified; redox-active V center; series; Molecular Biology; Cr; MOF; NH 3; Evolutionary Biology; neutron powder diffraction; NH 3 adsorption; Ecology; capacity; Cell Biology; General Chemistry; 540; Fe; 0104 chemical sciences; IV; Chemical sciences; material; Chemical Sciences; High Ammonia Adsorption; single-crystal X-ray diffraction; 0210 nano-technology; application; Developmental Biology; Biological Sciences not elsewhere classified

Ammonia (NH3) is a promising energy resource owing to its high hydrogen density. However, widespread application restricted by the lack of efficient and corrosion-resistant storage materials. Here, we report NH3 adsorption in series robust metal–organic framework (MOF) materials, MFM-300(M) (M = Fe, V, Cr, In). VIII, Cr) show fully reversible capacity for >20 cycles, reaching capacities 16.1, 15.6, 14.0 mmol g–1, respectively, at 273 K 1 bar. Under same conditions, MFM-300(VIV) exhibits highest uptake among this MOFs 17.3 g–1. In situ neutron powder diffraction, single-crystal X-ray electron paramagnetic resonance spectroscopy confirm that redox-active V center enables host–guest charge transfer, with VIV being reduced VIII oxidized hydrazine (N2H4). A combination inelastic scattering DFT modeling has revealed binding dynamics adsorbed within these afford comprehensive insight into MOF materials conversion NH3.