4. Conclusions
The adsorption of different small gas molecules allowed to clarify that
the addition of even small amounts of nanographite phase, targeting 1, 2
and 6 wt. % in the composites during the synthesis of UiO-66, resulted
in a marked (~ 30 %) increase in the porosity.
Ultramicropores narrower than 0.5 nm and pores wider than 0.7 nm were
formed and they probably have their origin in defective UiO-66 deposited
on the nanographite particles. These defects increased markedly the
adsorbed amounts of H2, CO2,
C2H4 and
C2H6 on the composites compared to those
on the parent UiO-66. Even though no direct dependence of the porosity
on the amount of nanographite in the composites was found when the
texture was analyzed by N2 adsorption, the increase in
the quanatity of hydrogen adsorbed with an increase in the nanographite
content might indicate the existence of ultramicropores only accessible
to H2. The isosteric heat of CO2adsorption at zero surface coverage almost linearly increased with the
nanographite content, suggesting the strong adsorption of
CO2 on the interface. In the case of H2,
its amount depended on the amount of nanographite suggesting the
extensive effects of the interface or the improved diffusion of
H2 to the smallest pores owing to the assembly of UiO-66
particle “walls” on the nanographite components. In the case of ethane
and ethylene adsorption, besides an increased porosity of the composite,
the interactions of these hydrocarbons with nanographite phase likely
contributed to the marked increase in the amount adsorbed on the
composite (42%). The trends in the heats of adsorption (higher on pure
UiO-66 than on the composite) suggested that these molecules adsorbed in
tetrahedral, octahedral, and defects-related pores. In particular, the
addition of nanographite appears as an especially interesting strategy
to increase H2 adsorption capacity of MOFs.
References
- Yuan S, Feng L, Wang K, Pang J, Bosch M, Lollar C, Sun Y, Qin J, Yang
X, Zhang P, Wang Q, Zou L, Zhang Y, Zhang L, Fang Y, Li Y, Zhou H-C.
Stable metal–organic frameworks: design, synthesis and applications.
Adv. Mater. 2018; 30: 170430.
- Baumann AE, Burns DA, Liu B, Thoi VS. Metal-organic framework
functionalization and design strategies for advanced electrochemical
energy storage devices. Comms Chem.2019; 2; 86-99.
- Fang Z, Bueken B, De Vos DE, Fischer RA. Defect-Engineered
Metal-Organic Frameworks/ Angew. Chem. Int. Ed. 2015: 54, 7234-7254.
- Shearer, GC, Vitillo, JG, Bordiga S,
Svelle S, Olsbye U, Lillerund KP. Functionalizing the
defects:postsynthetic ligand exchange in the metal organic framework
UIO-66. Chem mater. 2016; 28: 7190-7193.
- Taddei M, Wakeham RJ, Koutsianos A,
Andreoli E, Barron AR. Post-synthetic ligand exchange in
zirconium-based metal-organic frameworks: beware of the defects! Angew
Chem. Int. Ed. 2018; 57: 11706-11710.
- Shan B, McIntyre SM, Armstrong MR, Shen Y, Mu B. Investigation of
Missing-Cluster Defects in UiO-66 and Ferrocene Deposition into
Defect-Induced Cavities Ind. Eng. Chem. Res. 2018; 57, 14233-14241.
- Yuan L, Tian M, Lan J, Cao X, Wang X, Chai Z, Gibbson JK, Shi W.
Defect engineering in metal–organic frameworks: a new strategy to
develop applicable actinide sorbents. Chem Comm. 2018; 54: 370-373.
- Shen L, Liang R, Luo M, Jing F, Wu L. Electronic effects of ligand
substitution on metal-organic framework photocatalysts: the case study
of UiO-66. Phys. Chem. Chem. Phys. 215;17:117-121.
- Dissegna S, Epp K, Heinz WR, Kieslich G, Fischer RA. Defective
metal‐organic frameworks. Adv. Mater. 2018; 30: 1704501.
- J. M. Taylor, S. Dekura, R. Ikeda, H. Kitagawa, Chem. Mater. 2015, 27,
72286
- Cavka JH, Jakobsen S, Olsbye U, Guillou N, Lamberti C, Bordiga S,
Lillerud KP. A New Zirconium Inorganic Building Brick Forming Metal
Organic Frameworks with Exceptional Stability, J. Am. Chem. Soc. 2008,
130, 13850-13851.
- Katz MJ, Brown ZJ, Colon YJ, Siu PW, Scheidt KA, Snurr RQ, Hupp JP,
Farha OK, A facile synthesis of UiO-66, UiO-67 and their derivatives.
Chem. Commun. 2013, 49, 9449-9451.
- DeStefano MR, Islamogle T, Garibay SJ, Hupp JT, Farha, OK.
Room-temperature synthesis of UiO-66 and thermal modulation of
densities of defects. Chem. Mater. 2017:9: 1357-1361
- Grissom, TG, Driscoll, DM, Troya D, Sapienza, NS, Usov PM, Morris MJ,
Morris JR. Molecular-level insight into CO2 adsorption
on the Zirconium-based metal-organic framework, UiO-66: a combined
spectroscopic and computational approach. J. Phys. Chem, C. 2019; 123:
13731-13738.
- Abid HR, Tian H, Ang H-M, Tade MO, Buckley CE, Wang S. Nanosize
Zr-metal organic framework (UiO-66) for hydrogen and carbon dioxide
storage. Chen. Eng. J. 2012; 187: 415-420.
- Wu H, Chua YS, Krungleviciute V, Tyagi M, Chen P, Yildirim T, Zhou W.
Unusual and highly tunable missing-liker defects in zirconium
metal-organic frameworks UiO-66 and their important effects on gas
adsorption. J. Am. Chem. Soc. 2013; 135: 10525-10532.
- Cao Y, Zhao Y, Lv Z, Song F, Zhong Q. Preparation and enhanced
CO2 adsorption capacity of UiO-66/graphene oxide
composites. J. Ind.Eng. Chem. 2015;27:102-107.
- Noorpoor AR, Nazri Kudahi S. Analysis and study of CO2adsorption on UiO-66/graphene oxide composite using equilibrium
modeling and ideal adsorption solution theory (IAST). J. Environ.
Chem. Eng. 2016;4:1081-1091.
- Furukawa H, Gandara F, Zhang Y-B, Jiang J, Wueen WL,Hudson MR, Yaghi
OM. Water adsorption in porous metal-organic frameworks and related
materiuals. J. Am. Chem. Soc. 2014; 136: 4369-4382.
- Ghosh P, Colon YJ, Snurr RQ. Water adsorption in UIO-66: the
importance of defects. Chem Comm. 2014; 50-11329-11331.
- Zhao Q, Yuan W, Liang J, Li J. Synthesis an hydrogen storage studies
of metal organic framework UIO-66. Int. J. Hydrogen Energy. 2013; 38:
13104-13109.
- Lucier BEG, Zhang Y, Lee KJ, Lu Y, Huang Y. Grasping hydrogen
adsorption and dynamics in metal-organic framworks using2H solid-state NMR. Chem. Comm. 2016; 52: 7541-7544.
- Ren J, Langmi HW, North BC, Mathe M, Bessarabov D. Modulated synthesis
of zirconium -metalorganic framework (Zr-MOF) for hydrogen storage
applications. Int. J. hydrogen Energy. 2014; 39: 890-895.
- Zhang L, Li L, Hu E, Yang L, Shao K, Yao L, Jiang K, Cui Y, Yang Y, Li
B, Chen B, Qian G. Boosting ethylene/ethane separation with
copper(I)-chelated metal-organic frameworks through tailor-made
aperture and specific p-complexation. Adv. Sci..2020, 7:1901918.
- Wang X, Li L, Wang Y, Li J-R, Li J. Exploiting the pore size and
functionalization effects in UiO topology structures for the
separation of light hydrocarbons. CrystEngComm. 2017:19: 1729-1737.
- Chanut N, Wiersum AD, Lee U-H, Hwang YK, Ragon F, Chevreau H,
Bourrelly S, Kuchta B, Chang J-S, Serre C, Llewellyn PL. Observing the
effects of shaping on gas adsorption in metal organic frameworks. Eur.
J. Inorg. Chem. 2016; 27:4416-4423.
- Ramsahye NA, Gao J, Jobic H, llewellyn PL, Yang Q, Wiersum AD, Koza
MM, Guillerm V, Serre C, Zhong CL, Mauron G. Adsorption and diffusion
of light hydrocarbons in UiO-66(Zr): a combination of experimental and
modeling tools. J. Phys. Chem. C 2014; 118: 27470-27482.
- Policicchio A, Florent M, Attia MF, Whitehead DC, Jagiello J, Bandosz
TJ. Effect of the incorporation of functionalized cellulose
nanocrystals into UiO-66 on composite porosity and surface
heterogeneity alterations. Adv. Mater. Interfaces. 2020. In press.
- Giannakoudakis DA, Bandosz TJ. Defectous UiO-66 MOF Nanocomposites as
Reactive Media of Superior Protection against Toxic Vapors. Chem. Eng.
J. 2020, 3984, 123280
- Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F,
Rouquerol J, Sing KSW. Pure Appl. Chem. 2015; 87: 1051-1069.
- Seredych M, Jagiello J, Bandosz TJ. Complexity of CO2adsorption on nanoporous sulfur-doped carbons: Is surface chemistry an
important factor?Carbon 2014; 74: 207-2017
- Bandosz TJ, Putyera K, Jagiello J, Schwarz JA. Application of inverse
gas chromatography to the study of the surface properties of modified
layered minerals. Micro. Mater. 1993; 1: 73-79.
- Jagiello J, Olivier JP. Carbon slit pore model incorporating surface
energetical heterogeneity and geometrical corrugation. Adsorption
2013; 19:777-783.
- L. Czepirski, J. Jagiello. Virial-type thermal equation of gas—solid
adsorption. Chem. Eng. Sci. 1989; 44: 797-801
- Heck R, Shekhah O, Zybaylo O, Weidler PG, Friedrich F, Maul R, Wenzel
W, Woll C. Loading of two related metal-organic frameworks (MOFs),
[Cu2(bdc)2(dabco)] and
(Cu2(ndc)2(dabco)], with ferrocene.
Polymers 2011; 3L 1565-1574.
- Han Y, Liu M, Li K, Zuo Y, Wei Y, Xu S, Zhang G, Song C, Zhang Z, Guo
X. Facile synthesis of morphology and size-controlled zirconium
metal–organic framework UiO-66: the role of hydrofluoric acid in
crystallization. CrystEngComm. 2015; 17: 6434-6440.
- Clark CA, Heck KN, Powell CD, Wong MS. Highly Defective UiO-66
Materials for the Adsorptive Removal of Perfluorooctanesulfonate. ACS
Sustainable Chem. Eng. 2019: 7: 6619-6628.
- Everett DH, Powl JC. Adsorption in slit-like and cylindrical
micropores in the Henry’s law region. J. Chem. Soc. Faraday Trans.
1984; 619-621.
- Jagiello J, Kenvin J, Celzard A, Fierro V. Enhanced resolution of
ultra micropore size determination of biochars and activated carbons
by dual gas analysis using N2 and CO2with 2D-NLDFT adsorption models. Carbon 2019; 144: 206–215.
- Jagiello J, Kenvin J, Ania CO, Parra JB, Celzard A, Fierro V.
Exploiting the adsorption of simple gases O2 and
H2 with minimal quadrupole moments for the dual gas
characterization of nanoporous carbons using 2D-NLDFT models. Carbon
2020; 160: 164–175.
- Buckingham AD, Disch RL, Dunmur DA, Quadrupole moments of some simple
molecules, J. Am. Chem. Soc. 1968; 90: 3104-3107.
- Aguado S., Bergeret G., Daniel C., Farrusseng D. Absolute molecular
sieve separation of ethylene/ethane mixtures with silver zeolite A.
J. Am. Chem. Soc. 2012, 134, 14635−14637
- Ahmed A, Seth S, Purewal J, Wong-Foy AG, Veenstra M, Matzger AJ,
Siegel DJ. Exceptional hydrogen storage achieved by screening nearly
half a million metal-organic frameworks. Nat. Commun. 2019; 10: 1–9.