High capacity hydrogen adsorption in Cu(II) tetracarboxylate framework materials: the role of pore size, ligand functionalization, and exposed metal sites.
A series of isostructural metal-organic framework polymers of composition [Cu2(L)(H2O)2] (L= tetracarboxylate ligands), denoted NOTT-nnn, has been synthesized and characterized. Single crystal X-ray structures confirm the complexes to contain binuclear Cu(II) paddlewheel nodes each bridged by four carboxylate centers to give a NbO-type network of 64.82 topology. These complexes are activated by solvent exchange with acetone coupled to heating cycles under vacuum to afford the desolvated porous materials NOTT-100 to NOTT-109. These incorporate a vacant coordination site at each Cu(II) center and have large pore volumes that contribute to the observed high H2 adsorption. Indeed, NOTT-103 at 77 K and 60 bar shows a very high total H2 adsorption of 77.8 mg g(-)- equivalent to 7.78 wt% [wt% = (weight of adsorbed H2)/(weight of host material)] or 7.22 wt% [wt% = 100(weight of adsorbed H2)/(weight of host material + weight of adsorbed H2)]. Neutron powder diffraction studies on NOTT-101 reveal three adsorption sites for this material: at the exposed Cu(II) coordination site, at the pocket formed by three {Cu2} paddle wheels, and at the cusp of three phenyl rings. Systematic virial analysis of the H2 isotherms suggests that the H2 binding energies at these sites are very similar and the differences are smaller than 1.0 kJ mol-1, although the adsorption enthalpies for H2 at the exposed Cu(II) site are significantly affected by pore metrics. Introducing methyl groups or using kinked ligands to create smaller pores can enhance the isosteric heat of adsorption and improve H2 adsorption. However, although increasing the overlap of potential energy fields of pore walls increases the heat of H2 adsorption at low pressure, it may be detrimental to the overall adsorption capacity by reducing the pore volume.
Lin
Xiang
X
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Telepeni
Irvin
I
Blake
Alexander J
AJ
Dailly
Anne
A
Brown
Craig M
CM
Simmons
Jason M
JM
Zoppi
Marco
M
Walker
Gavin S
GS
Thomas
K Mark
KM
Mays
Timothy J
TJ
Hubberstey
Peter
P
Champness
Neil R
NR
Schröder
Martin
M
D000327:Adsorption; D002264:Carboxylic Acids / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006859:Hydrogen / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry; D008024:Ligands; D008958:Models, Molecular; D033363:Neutron Diffraction; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D002264:Carboxylic Acids; D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper; D006859:Hydrogen; D006861:Hydrogen Peroxide