Experimental and Theoretical Studies of Gas Adsorption in Cu3(BTC)2: An Effective Activation Procedure
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- 作者：Jinchen Liu ; Jeffrey T. Culp ; Sittichai Natesakhawat ; Bradley C. Bockrath ; Brian Zande ; S. G. Sankar ; Giovanni Garberoglio ; J. Karl Johnson
- 刊名：Journal of Physical Chemistry C
- 出版年：2007
- 出版时间：July 5, 2007
- 年：2007
- 卷：111
- 期：26
- 页码：9305 - 9313
- 全文大小：249K
- 年卷期：v.111,no.26(July 5, 2007)
- ISSN：1932-7455
文摘
We have improved the activation process for CuBTC [Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate] byextracting the N,N-dimethylformamide-solvated crystals with methanol; we identify material activated in thisway as CuBTC-MeOH. This improvement allowed the activation to be performed at a much lower temperature,thus greatly mitigating the danger of reducing the copper ions. A review of the literature for H2 adsorptionin CuBTC shows that the preparation and activation process has a significant impact on the adsorption capacity,surface area, and pore volume. CuBTC-MeOH exhibits a larger pore volume and H2 adsorption amountthan any previously reported results for CuBTC. We have performed atomically detailed modeling tocomplement experimentally measured isotherms. Quantum effects for hydrogen adsorption in CuBTC werefound to be important at 77 K. Simulations that include quantum effects are in good agreement with theexperimentally measured capacity for H2 at 77 K and high pressure. However, simulations underpredict theamount adsorbed at low pressures. We have compared the adsorption isotherms from simulations withexperiments for H2 adsorption at 77, 87, 175, and 298 K; nitrogen adsorption at 253 and 298 K; and argonadsorption at 298 and 356 K. Reasonable agreement was obtained in all cases.