High capacity hydrogen and nitric oxide adsorption and storage in a metal-organic framework

Transcription

1 High capacity hydrogen and nitric oxide adsorption and storage in a metal-organic framework Bo Xiao, 1 Paul S. Wheatley, 1 Xuebo Zhao, Ashleigh J. Fletcher, Sarah Fox Adriano G Rossi, Ian L. Megson, 3 S. Bordiga, 5 L. Regli, 5 K. Mark Thomas,, * and Russell E. Morris 1, * 1 EaStChem School of Chemistry, University of St Andrews, Purdie Building, St. Andrews, KY1 9ST, UK Northern Carbon Research Laboratories, School of Natural Sciences, Bedson Building University of Newcastle upon Tyne, Newcastle upon Tyne, NE1 7RU, UK 3 UHI Millennium Institute, Beechwood Business Park North Inverness IV 3BL, UK Queen's Medical Research Institute, University of Edinburgh, 7 Little France Crescent, Edinburgh, EH1 TJ, UK 5 Dipartimento di Chimica IFM and NIS Centre of Excellence Univeristà di Torino, Via P. Giuria 7, I-15 Torino, Italy Supplementary information (1) Synthesis of HKUST-1 In a typical synthesis, 3. mmol of Cu(NO 3 ).3H O (.71g) and. mmol of benzene 1,3,5-tricarboxylic acid (.1g) was mixed with 1 ml of EtOH/H O (5:5) solution in a Teflon-lined autoclave. The mixture was stirred for 3 minutes at ambient temperature prior to be heated in an oven preheated at 33K, followed by heated at 33K for hours. After crystallization the autoclave was naturally cooled down to room temperature. The yield was sonicated for 5- minutes in a solution of EtOH/H O (5:5). Large turquoise blue crystals were isolated by Buchner filtration and dried in air for one day. () NO adsorption/desorption of HKUST-1 The adsorption/desorption of nitric oxide gas in HKUST-1 was measured using a gravimetric adsorption system. A thermal stabiliser is used in a microbalance to eliminate the effect from external environment. The microbalance has a sensitivity of.1 microgram and reproducibility of.1% of the load. ~ mg of sample was initially outgassed at K under 1 x - mbar for hours until no further weight losses were observed. The sample temperature was then decreased to 9 K and stabilised by a circulation water bath with temperature accuracy +-. K. The counterbalance was kept at the same temperature as the sample to minimize the influence of temperature difference on weight readings. The sample temperature was monitored using a K type of thermocouple, located close to sample bucket (<5 mm). The variation in sample temperature was minimal (<. K) throughout the experiment. NO gas was introduced into the system until the desired pressure was achieved. The mass uptake of the sample was measured as a function of time. Each adsorption point was set to - hours. This allows adsorption equilibrium to achieve. Adsorption isotherm was obtained by increasing the pressure and recording the mass gain of the S1

2 sample at equilibrium. Desorption of nitric oxide gas adsorbed in the samples was performed by gradually decreasing the system pressure to a desired value (until x - mbar). (3) Powder X-ray diffraction of HKUST-1 X-ray diffraction pattern of HKUST-1 was collected on a STOE STADIP diffractometer operating in transmission mode using Cu Kα1 radiation (λ=1.5). HTT 373K under VAC after adsorption of N and CO a.u a.u as synthesis a.u from crystal data (Ian D Williams et al. Science 1999 vol.,11.) θ Figure S.1 A comparison of powder XRD patterns of HKUST-1 after activations to remove guest molecules (top), as made (middle) and a comparison with the theoretical pattern from the single crystal data (bottom). () FTIR of HKUST-1 Infrared spectrum of HKUST-1 was measured on a PerkinElmer Spectrum GX FT-IR system with resolution.cm -1 using KBr disc with sample ~3 wt%. S

3 %T cm-1 Figure S. FT-IR spectrum of HKUST-1. (5) TG analysis of HKUST-1 Samples were examined by thermogravimetric analysis (TGA) using a TA Instruments SDT 9 simultaneous DTA TGA thermogravimetric analyser. Samples were heated in an alumina crucible at a rate of Kmin -1 to a maximum temperature 73K in a flowing atmosphere of argon ( ml min -1 ). Re-calcined aluminium oxide was used as the reference material. Sample: HKUST-1 Size:.13 mg Method: Comment: heating rate oc until oc under N 5 TGA-DTA File: A:\Hkust_1 Operator: bx Run Date: 1-Oct-5 11: C.15mg 1.1mg (33.3%) Weight (mg) C 3.1mg 9.7 C.91mg.7mg (5.9%) 1.1mg (.%) 1 Temperature ( C) Universal V.5H TA Instruments S3

4 Figure S.3 TGA analysis of HKUST-1 (). Hydrogen adsorption experiments Hydrogen adsorption experiments were carried out at the University of Newcastle. 1 1 Amount adsorbed/mmolg Adsorption on HB-1(sample1) in IGA1 Desorption from HB-1(sample1) in IGA1 Pressure/mbar Figure S Ad/desorption isotherms for H on HKUST-1 (Code: HB-1 sample1) in IGA1 at 77 K Amount adsorbed/mmolg H on HB-1(sample1) first in IGA1 H on HB-1 (sample1) second in IGA1 p/mbar Figure S5 Repeat isotherms for H on HKUST-1 (HB1sample1) at 77 K in IGA1 S

5 H amount adsorbed/ mmol g sample in IGA1 H adsorption on HB1 in IGA1 H desorption on HB1 in IGA1 H adsorption on HB1 in IGA1 (repect) H desorption on HB1 in IGA1 (repeat) P/ mbar Figure S H adsorption isotherms on HKUST-1 HB1(sample) at 77 K in IGA1(High Pressure) 1 H amount adsorbed/ mmol g P/ mbar sample1 sample H adsorption on HB1 at 77 K in IGA1 Figure S7 Comparison of H adsorption isotherms on sample1 and sample in IGA1 Sample repeat studies S5

6 1 H adsorption on HB1 (sample) at 77 K in IGA Amount adsorbed/ mmol g -1 adsorption on fresh HB-1 in IGA first desorption on fresh HB-1 in IGA first adsorption on fresh HB-1 in IGA second desorption on fresh HB-1 in IGA second Pressure/ mbar Figure S Repeated isotherms in IGA (sample) 1 HB-1 (sample) at 77 K n/mmolg -1 ndad ndde nhad nhde p/mbar nd/nh p/mbar Figure S9 D /H adsorption isotherms in IGA (sample) S

7 1 H adsorption on HB1(sample) at 77K n/mmolg p/mbar ads/des in IGA1 ads/des in IGA n=11.5 mmolg -1 in IGA1 at mbar n=11. mmolg -1 in IGA at mbar diff=1.1% Figure S H adsorption isotherms on HB-1 (sample) at 77 K H uptake/ w% Yaghi, w%, volumetric, surface excess NCRL, w%, gravimetric, in IGA1. 1 P/ bar Figure S11 Comparison of HB1(sample) and those from Wong-Foy, A.G.; Matzger, A.J.; Yaghi, O.M. J. Am. Chem. Soc, 1, 39. The results reported in this paper are in red, those of Wong-Foy et al are in black. S7

8 .5. H adsorption/ w% Lee, w%, volumetric Prestipino, w%, volumetric Yaghi1, w%, gravimetric Yaghi, w%, volumetric, surface excess NCRL, w%, gravimetric, in IGA P/ bar Figure S1 A comparison of all the literature values of H adsorption and those reported in this paper (NCRL - blue diamonds). There reference citations for the other data shown are (a) Lee, J.-Y.; Li, J.; Jagiello, J. J. Solid State. Chem. 5, 17, 57, (b) Prestipino, C.; Regli, L.; Vitillo, J.G.; Bonino, F.; Damin, A.; Lamberti, C.; Zecchina, A.; Solari, P.L.; Kongshaug, K.O.; Bordiga, S. Chem. Mater., 1, 1337 (c) Rowsell, J.L.C; Yaghi, O.M. J. Am. Chem. Soc, 1, 13, (d) Wong-Foy, A.G.; Matzger, A.J.; Yaghi, O.M. J. Am. Chem. Soc, 1, 39. S