High ammonia adsorption in MFM-300 materials: Dynamics and charge transfer in host–guest binding

DOI: 10.1021/jacs.0c11930

Authors: Xue Han (University of Manchester) , Wanpeng Lu (University of Manchester) , Yinlin Chen (University of Manchester) , Ivan Da Silva (ISIS Facility) , Jiangnan Li (University of Manchester) , Longfei Lin (University of Manchester) , Weiyao Li (University of Manchester) , Alena M. Sheveleva (University of Manchester) , Harry G. W. Godfrey (University of Manchester) , Zhenzhong Lu (University of Manchester) , Floriana Tuna (University of Manchester) , Eric J. L. Mcinnes (University of Manchester) , Yongqiang Cheng (Oak Ridge National Laboratory) , Luke L. Daemen (Oak Ridge National Laboratory) , Laura J. Mccormick Mcpherson (Advanced Light Source) , Simon J. Teat (Advanced Light Source) , Mark D. Frogley (Diamond Light Source) , Svemir Rudic (ISIS Facility) , Pascal Manuel (ISIS Facility) , Anibal J. Ramirez-Cuesta (Oak Ridge National Laboratory) , Sihai Yang (University of Manchester) , Martin Schroeder (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: February 2021
Diamond Proposal Number(s): 23782

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

Journal Keywords: Adsorption; Molecules; Metal organic frameworks; Physical and chemical processes; Materials

Diamond Keywords: Hydrogen Storage

Subject Areas: Materials, Chemistry


Instruments: B22-Multimode InfraRed imaging And Microspectroscopy

Other Facilities: TOSCA/WISH at ISIS

Discipline Tags:

Material Sciences Metallurgy Metal-Organic Frameworks Chemistry Organometallic Chemistry

Technical Tags:

Spectroscopy Infrared Spectroscopy Synchtron-based Fourier Transform Infrared Spectroscopy (SR-FTIR)