WO2020060887A2 - Réseau organométallique inspiré d'une enzyme - Google Patents

Réseau organométallique inspiré d'une enzyme Download PDF

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WO2020060887A2
WO2020060887A2 PCT/US2019/051211 US2019051211W WO2020060887A2 WO 2020060887 A2 WO2020060887 A2 WO 2020060887A2 US 2019051211 W US2019051211 W US 2019051211W WO 2020060887 A2 WO2020060887 A2 WO 2020060887A2
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mof
composition
activity
catalyst
products
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Omar M. Yaghi
Gabor A. Somorjai
Jayeon BAEK
Bunyarat RUNGTAWEEVORANIT
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The Regents Of The University Of California
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/003—Catalysts comprising hydrides, coordination complexes or organic compounds containing enzymes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • MOFs metal-organic frameworks
  • the metal binding ligands bearing an imidazole unit in the copper active site of pMMO can be mirrored in a synthetic system by post-synthetic modification of MOFs 32 34 . Once these metal-binding ligands are in place, metalation with the desired configuration can be accomplished 35 ’ ⁇ 56 .
  • MOFs can be used as a backbone for the creation of an enzyme-like active site by installing biologically relevant imidazole moieties, then subsequently metalating these ligands to incorporate a variety of reactive metal-oxygen complexes within the framework.
  • the resulting catalysts are capable of highly selective catalytic activity, typically under isothermal conditions.
  • the modularity in choosing the metals and imidazole-based ligands in this approach provides a direct route to systematically tune the reactivity of the active site.
  • metalation of iron and zinc in MOF bearing imidazole moieties can be employed to have structural similarity to sMMO and CAII, respectively where sMMO is a methanotroph that oxidizes methane to form methanol using atmospheric oxygen and carbonic anhydrase (CA) is a ubiquitous zinc metalloenzyme that catalyzes the reversible hydration of carbon dioxide.
  • CA carbonic anhydrase
  • Both methane and carbon dioxide are challenging gas molecules to catalyze under mild reaction conditions; this invention provides for converting both molecules to useful chemicals via enzyme-inspired MOFs, with diverse applications such as shale gas conversion to methanol, carbon sequestration, etc.
  • the invention provides a composition comprising a metal-organic framework (MOF) catalyst comprising metalated azole ligands which form a reactive metal- oxygen complex within the MOF.
  • MOF metal-organic framework
  • the MOF is metalated with Cu, Fe or Zn;
  • the ligands are imidazole-, pyrazole- and/or triazole ligands, preferably imidazole ligands, preferably selected from L-histidine, 4-imidazoleacry!ic acid and 5- benzimidazolecarboxyiic acid;
  • the MOF is selected from MOF-808, 23 ⁇ 40 4 (0H) 4 (BTC) 2 (HC00) 5 (H 2 0), (OFF)i ,
  • the composition provides catalytic activity selected from methane oxygenase, carbonic anhydrase and alcohol dehydrogenase;
  • the composition provides methane oxygenase activity, and comprises reactants and/or products of the activity [methane, N 2 0, 0 2 , NAD(P)H to methanol, N 2 , water, and NAD(P)];
  • the composition provides carbonic anhydrase activity, and comprises reactants and/or products of the activity (carbon dioxide, water to carbonic acid);
  • the composition provides alcohol dehydrogenase activity, and comprises reactants and/or products of the activity (alcohol (e.g ethanol), NAD + to aldehyde (e.g. acetaldehyde),
  • alcohol e.g ethanol
  • NAD + to aldehyde e.g. acetaldehyde
  • the invention provides methods of making the subject compositions, such as comprising metalating the ligands to incorporate reactive metal-oxygen complexes within the MOF.
  • the invention provides methods of using the subject compositions such as forming a mixture of the catalyst and reactants under conditions wherein the catalyst catalyzes a reaction of the reactants to form products.
  • the reactants/products comprise methane/methanol, carbon
  • the invention encompasses all combination of the particular embodiments recited herein, as if each combination had been laboriously recited.
  • FIG. 1 Figures la-c, Design and synthesis of the catalysts bearing copper-oxygen complexes in MOF-808 for methane oxidation to methanol, a, Structure of MOF-808. b, Pseudohexagonal pore opening of MOF-808. c, Synthesis of the catalysts comprising the replacement of formate with imidazole-containing ligands and meta!ation with Cu(I).
  • Atom labeling scheme C, black; O, red; N, green; Cu, orange; Zr, blue polyhedra. H atoms are omitted for clarity. Orange spheres represent the space in the tetrahedral cages.
  • Figures 2a-d a, Average with standard error of methanol productivity of MOF-808- His-Cu, MOF-808-Iza-Cu and MOF-808-Bzz-Cu. b, Ex-situ N K-edge XANES spectra of MOF-808-Bzz, as-synthesized MOF-808-Bzz-Cu and MOF-808-Bzz-Cu after the reactions with Fie, 3% N 2 0/He, CH 4 and 3% steam/TIe. c, Ex-situ Cu K-edge XANES spectra ofMOF-808- Bzz-Cu after the reactions with He, 3%N 2 0/He, C3 ⁇ 4 and 3% steam/He. d, Resonance Raman spectra of MOF-80S-Bzz-Cu synthesized using i6 0 2 and 18 G 2 with 407 ran laser. Note that i8 G 2 spectrum contain some 16 0 2 contamination.
  • FIG 3 DFT optimized structure of the proposed active site in MOF-808-Bzz-Cu. From ICP, 1 H NMR, and N K-edge XANES, each N atoms of the ligands is coordinated to one copper atoms. However, copper in bis(/i--oxo) dicopper is known to be four-coordinated '.
  • the fourth ligand coordinating to copper is a neutral ligand such as water or NN- dimethyiformamide molecules as we observed the latter molecule in the ! H NMR spectra of the digested samples after activation (only the optimized structure of the active site is shown, while the remaining atoms of the MOF-808 are omitted for clarity).
  • Atom labeling scheme C, black; O, red; N, green; H, white; Cu, orange.
  • FIG. 5a-5b SEM images of (a) MOF-808-His and (b) MOF-808-His-Cu.
  • FIG. 7a-7b SEM images of (a) MOF-808-Iza and (b) MOF-808-Iza-Cu.
  • Figure 9a-b SEM images of (a) MOF-808-Bzz and (b) MOF-808-Bzz-Cu.
  • MOF-808 is composed of 12-connected cuboctahedron Zr 6 0 4 (0H) 4 (-C00)i 2 secondary building units (SBUs) linked to the other SBUs by six benzenetricarboxylates (BTC) with three above and three below the ring of formates to form tetrahedral cages (Fig. la). When linked, these cages form an adamantane-shaped pore with formate, water and hydroxide molecules completing the coordination spheres of Zr(IV) and pointing into the pseudohexagonal pore openings (Fig. lb).
  • microcrystalline MGF-808 to allow for a facile diffusion of substrates during post-synthetic modifications and catalysis .
  • metal binding ligands comprising biologically relevant imidazole units for incorporation into the framework to demonstrate the modularity of our system and to study the effect of how ligand rigidity influences the catalytic properties.
  • Metal binding ligands including L-histidine (His), 4- imidazoleacryiic acid (Iza) and 5-benzimidazolecarboxylic acid (Bzz) were incorporated into the framework by heating MOF-808 in saturated solutions of these metal binding ligands to produce MOF-808-L with -L being -His, -Iza and -Bzz, respectively.
  • the successful substitution of formate with these ligands in the MOF was confirmed by *H nuclear magnetic resonance (NMR) of the digested samples (Supplementary Section 2.1).
  • MOF-808-His [Zr 6 0 4 (0H)4(BTC)2(ffis)3.5(0H) 2.5 (H 2 0)2.5]
  • MOF-808-Iza [Zr 6 0 4 (0H) 4 (BTC)2 (Iza) 3.7 (HCOO) i .6 (OH) 0.7 (13 ⁇ 40) O.7 ]
  • MOF-808-Bzz [Zr 6 0 4 (0H) 4 (BTC) 2 (Bzz) 3.4 (HC00) i 6 (OH) s (H2O) ] .
  • MOF-808-Bzz-Cu Inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis performed on these catalysts indicates the Cu/Zr 6 molar ratios of 4.9, 6.0 and 7.1 for MOF-808-His-Cu, MOF-808-lza-Cu and MOF-808-Bzz-Cu, respectively (Table 1).
  • Methane oxidation was conducted with an isothermal series of treatments at 150 °C.
  • 100 g of MOF-808-L-Cu catalyst was pretreated in He flow to remove residual solvents (i.e., MeCN and water) at temperatures starting from room temperature to 150 °C at a ramping rate of 3 °C min 1 .
  • the catalyst was treated with 3% N 2 0/He for 2 h at 150 °C followed by purging the catalyst with He for 30 min.
  • the catalyst was subsequently exposed to a flow of CFL for 1 h at 150 °C for methane activation.
  • the average methanol productivity corresponds to 31.7 ⁇ 13.0, 61.8 ⁇ 17.5 and 71.8 ⁇ 23.4 pmol gMOF-sos-L-cu 1 for MOF-808-His- Cu, MOF-808-Iza-Cu, and MOF-808-Bzz-Cu, respectively; indicating that the MOF-808-Bzz- Cu has the highest methanol productivity among three catalysts.
  • MOF-808-His-Cu exhibited lower activity which is more likely due to lower number of catalytically active copper-oxygen species (-43% lower turno ver number compared to MOF-808-Bzz-Cu), attributed to the flexibility of histidine ligand.
  • methanol and water were observed as products during methanol desorption at a temperature below or equal to 150 °C. This was confirmed by gas chromatographs equipped with flame ionization and thermal conductivity detectors and a mass analyzer. Above this temperature, we observed increased methanol production with temperature, as we expected due to improved methanol extraction efficiency. However, C0 2 was also observed as a byproduct from the overoxidation of the methanol generated.
  • MOF-808-L and Cut (Cu(I) precursor we did not observe any products in the experiments performed on MOF-808-L and Cut (Cu(I) precursor.
  • the catalysts are composed of a mixture of Cu(I) and Cu(II) species.
  • the He pretreatment at 150 °C resulted in a decrease in the white line intensity at 8998 eV along with an increase in the absorption peak intensity at 8984 eV showing that the majority of Cu(II) is reduced to Cu(I) by autoreduction.
  • 43 ’ 46 The spectrum recorded after 3% N 2 0/He at 150 °C exhibits oxidation of Cu(I) to Cu(II), indicative of the formation of the active copper oxygen species. After the reaction with methane at 150 °C, the peak intensity of Cu(I) at 8984 eV increased while the white line intensity decreased indicating the reduction of Cu(II) to Cu(I).
  • MOF-808-Iza-Cu also shows distinctive changes in the oxidation state of copper following the same trend through the course of the catalytic process as described for MOF-808-Bzz-Cu.
  • MOF-808-His-Cu shows minor intensity changes, consistent with the lower methanol productivity as previously described (Fig. 2a).
  • UV-Vis DRS was performed. Background subtracted UV-Vis DRS spectra of the as-synthesized samples show the absorption band centered at -400 ran After 3% N 2 G/He treatment at 150 °C, we observed the increase of this absorption band (Supplementary Section 5.1) corresponding to oxygen-to-metal charge-transfer transition 49-52 . To definitively characterize this copper-oxygen species, we turned to resonance Raman spectroscopy measurement because each copper-oxygen species have characteristic Raman shifts 16,1 ' (Supplementary Section 8).
  • Figure 2d shows the isotope-dependent Raman peaks at -560 and -640 cm 1 by using an excitation wavelength of 407 nm which is resonant at the charge-transfer band. These peaks are assigned to Cu- -O bonds vibration in the core breathing mode of bis(/ oxo) dicopper species (Supplementary Information, Section S6) In the 0 2 -labeled samples, these Raman peaks are shifted to -545 cm and -630 cm .
  • FIG. 4 depicts the k -weighted and Fourier transforms without phase correction of the extended X-ray absorption fine structure (EXAFS) data measured at the Cu K-edge of the MOF- 808-Bzz-Cu.
  • the spectra were recorded after the successive treatment with (a) He, (b) 3%
  • the bond valence sum analysis (Supplementary Tables 5-7) further indicates the actual charge being close to 2-fold 44 ’ 56 ’ 57 .
  • Oxidation of the catalyst in 3% N 2 0/He at 150 °C leads to 0.8 increase of the Cu-N/(0) coordination while its distance remains at 1.94 A indicating the additional formation of bis( /-oxo) dicopper species.
  • Cu-N/(0) coordination increases by 0.6.
  • Cu-N/(0) coordination in MOF-808-His-Cu and MOF-808-Iza-Cu remains similar after treatment with methane and steam.
  • MOF-8O8 was synthesized following the reported procedure ⁇ 58 .
  • 1,3,5-benzenetricarboxylic acid (210 mg) and Zr0Cl 2 -8H 2 0 (970 g) were dissolved in a solution containing DMF (30 mL) and formic acid (30 mL).
  • the bottle was sealed and heated in a 100 °C isothermal oven for a day.
  • White powder was collected by centrifugation (8,000 rpm, 3 min), washed with DMF 3 times (60 mL x 3) over a 24 h period and with acetone 3 times (60 mL x 3) over a 24 h period.
  • Pretreatment of the catalyst was conducted under He (30 seem) at 150 °C (3 °C/min) for 1 h.
  • the catalyst was then oxidized using 3% N 2 0/He flow (30 seem) at 150 °C for 2 h.
  • CH 4 (30 seem) was flowed into the catalyst for 1 h.
  • 3% steam/He (30 see ) was flowed into the catalyst. All lines were heated at 120 °C to prevent condensation.
  • the outlet of the reactor was analyzed by gas chromatography (Model: GC-2014, Shimadzu Co.). The measurement started 3 min after opening the valve to 3% steam/He.
  • the reactants and products were separated using HayeSep R 80/100 stainless steel packed column (12 ft, 1/8 in OD, 2mm ID)
  • the water and C0 2 were monitored using a thermal conductivity detector and methanol was monitored using a flame ionization detector
  • X-ray absorption spectroscopy (XAS). N K-edge X-ray absorption spectra were collected at beamline 8 0.1, an undulator beamline with energy range of 80-1200 eV of the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL). Its spherical gratings monochromator delivers 1012 photons/second with linear polarization with a resolving power up to 6000. The experimental energy resolution is better than 0.15 eV. Experiments were performed at room temperature.
  • ALS Advanced Light Source
  • LBNL Lawrence Berkeley National Laboratory
  • a linear, sloping background is removed by fitting a line to the fiat low energy region of the XAS spectrum, i.e., at energies below any absorption peaks 3)
  • the spectrum is normalized by setting the flat low energy region to zero and the post edge to unity (unit edge jump).
  • Cu K-edge X-ray absorption spectroscopy data were collected at the Advanced Light Source (ALS) bending-magnet beamline 10.3.2 (2.1-17 keV) with the storage ring operating at 500 mA and 1.9 GeV, using a Si(l 11) monochromator and adjustable pre-monochromator slits All data were collected at room temperature (24 °C) in fluorescence mode at the Cu K- edge (8980.48 eV). The incoming X-ray intensity ([ ⁇ >) was measured in an ion chamber and the fluorescence emission with a seven element LN 2 cooled Ge solid state detector (Canberra) using XI A electronics.
  • a Cu foil was used to calibrate the monochromator, with 1 st derivative maximum set at 8980.48 eV 59 and an internal IQ glitch (present in all spectra) was used to calibrate the data.
  • the MOF-808-L-Cu samples were cooled down with a He purge after each gas treatment in a 316-stainless steel reactor.
  • the reactor containing the sample was sealed with a Swagelok valve and moved to an argon-filled glovebox (H 2 0 and 0 2 levels ⁇ 1 ppm).
  • the sample was unloaded and sealed with Kapton tape for ex-situ measurements.
  • XANES spectra were recorded in fluorescence mode by continuously scanning the Si (111) monochromator (Quick XAS mode) from 8,880 to 9,020 eV, with 0.3 eV steps in the XANES region. All data were processed using the Lab VIEW " custom BL 10.3.2 software to perform dead time correction, energy calibration, and glitch removal with detail procedure described elsewhere 60 . XANES spectra were processed with Athena software 61 to find first derivative peak (E 0 ), pre-edge background substruction and post-edge normalization, align and merge the spectra.
  • the sample was loaded into a thin-wa!l quartz capillary'- tube and sealed with epoxy glue for the measurements. All spectra were collected using the 407 ran light with the power density of 3.1 W/cm .
  • the Raman scattering was collected using a Spex 1401 double grating spectrograph and liquid nitrogen cooled Roper Scientific LN/CCD 1100 controlled by ST 133 controller. The measured Raman shifts were calibrated by using Raman peaks of cyclohexane.
  • DFT calculations were geometrically optimized at the density functional theory (DFT) in gas phase using spin-unrestricted B3LYP functional 63,64 as implemented in Gaussian 16 (revision A03) without symmetry constraints 65 .
  • the 6-31G basis sets were employed for C and H atoms while 6-31 lG(d) basis sets were used for Cu, N and O atoms.
  • Numerical integrations were performed on an ultrafine grid.
  • O atoms of carboxylate groups of the metal binding ligands were frozen to simulate the rigidity of the framework. Minima of all geometry-optimized structures were verified by having no imaginary frequency found from analytical frequency calculation performed at the same level of theory.
  • MOF-808-His A saturated solutio of 1-histidine was prepared by dissolving L ⁇ histidine (93 mg) in water (8 mL) in a 20 mL vial in an 85 °C isothermal oven. MGF-808 (160 mg) was suspended by sonication in the saturatio solution of L-histidine and the suspension was heated in an 85 °C isothermal oven overnight. The reaction was allowed to cool to about 50 °C while the supernatant was carefully removed prior to the recrystallization of L-histidine.
  • MOF-808-Iza A solution of 4-imidazole acrylic acid was prepared by dissolving 4- imidazole acrylic acid (6 g) in DMSO (70 mL) in a 100-mL bottle in a 100 °C isothermal oven. MOF-8Q8 (1 g) was suspended by sonication in the solution of 4-imidazole acrylic acid and the suspension was heated in a 100 °C isothermal oven overnight. The reaction was allowed to cool to room temperature. White powder was collected by centrifugation (8,000 rpm, 3 min), washed with DMSO 5 times (80 mL x 5) over 3 days and with acetone (80 mL x 5) over 3 days.
  • the MOF backbone was first assigned and refined anisotropically.
  • the refinement on the disordered p 3 -() (02A/ ⁇ 2B, 03A/03B) and oxygen from coordinating ligand (04A/04B) was conducted according to the previous report. 5
  • electron density peaks were assigned from the framework outwards - in other words, form the coordinating carboxylate group to the ligand’s dangling‘tail 5 . Due to the flexibility of the binding ligands as well as the proximity to a very 7 high symmetry site, their positions are largely disordered so that only part of the ligand in each case can be clearly assigned.
  • the UV-Vis diffuse reflectance spectroscopy (DRS) spectra of MOF-808-L, MOF-808- L-Cu and MOF-808-L-Cu were collected using Shimadzu model UV-2450 spectrometer equipped with an integrating sphere model ISR-2200.
  • the MOF-808-L-Cu samples treated under 3% N 2 0/He at 150 °C for 1 h in a 316 stainless steel reactor was cooled down with He purge and is closed with Swagelok valve, moved to an argon-filled glovebox, and transferred into the home-built stainless steel vacuum cell for UV-Vis diffuse reflectance experiments. 6
  • the spectra of MOF-808-L-Cu and MOF-808-L-Cu were subtracted using their corresponding MOF- 808-L spectra.
  • the solid was collected by centrifugation, dried overnight, transferred to an Argon-filled glovebox and washed with anhydrous ACN 5 times (2 mL x 5) over 3 days.
  • the sample was dried under dynamic vacuum overnight at room temperature, and the dried solid was transferred to the glovebox.
  • the MOF-808-L-Cu samples in the 316 stainless steel reactor was cooled down with a He purge after each gas treatment and is closed with Swagelok valve, and moved to the argon- filled glovebox.
  • the sample was loaded into a thin-wall quartz capillary tube and sealed with epoxy glue.
  • the Cu-0 complexes along with their metal binding ligands were extracted from the models and carboxylate groups of metal binding ligands were neutralized with protons.
  • the clusters were geometrically optimized at the density functional theory 7 (DFT) in gas phase using spin-unrestricted B3LYP functional as implemented in Gaussian 16 (revision A03) without symmetry constraints.
  • DFT density functional theory 7
  • the 6-31G basis sets were employed for C and H atoms while 6-31 lG(d) basis sets were used for Cu, N and O atoms.
  • Numerical integrations were performed on an ultrafme grid.
  • O atoms of carboxylate groups of the metal binding ligands were frozen to simulate the rigidity of the framew 7 ork. Minima of all geometry- optimized structures were verified by having no imaginary frequency found from analytical frequency calculation performed at the same level of theory.
  • N K-edge X-ray absorption spectra were collected at beamline 8.0.1, an undulator beamline with energy range of 80-1200 eV of the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL). Its spherical gratings monochromator delivers 1012 photons/second with linear polarization with a resolving power isp to 6000. The experimental energy resolution is better than 0.15 eV. Experiments were performed at room temperature. All the spectra were collected in both total-electron-yield (TEY) and total- fluorescence-yield (TFY) modes simultaneously, corresponding to a probe depth of about 10 nrn and 100 nm, respectively.
  • TEY total-electron-yield
  • TFY total- fluorescence-yield
  • Cu K-edge X-ray absorption spectroscopy data were collected at the Advanced Light Source (ALS) bending-magnet beamline 10.3.2 (2.1 -17 keV) with the storage ring operating at 500 mA and 1.9 GeV, using a Si(l 1 1) monochromator and adjustable pre-monochromator slits. 12 All data were collected at room temperature (24 °C) in fluorescence mode at the Cu K-edge (8980.48 eV). The incoming X-ray intensity (I 0 ) was measured in an ion chamber and the fluorescence emission with a seven element LN 2 cooled Ge solid state detector (Canberra) using XIA electronics.
  • ALS Advanced Light Source
  • a Cu foil was used to calibrate the monochromator, with 1 sl derivative maximum set at 8980.48 eV i3 and an internal To glitch (present in all spectra) was used to calibrate the data.
  • the MOF-808-L-Cu samples were cooled down with a He purge after each gas treatment in a 316- stainless steel reactor.
  • the reactor containing the sample was sealed with a Swagelok valve and moved to an argon-filled glovebox (H 2 0 and 0 2 levels ⁇ 1 ppm).
  • the sample was unloaded and sealed with Kapton tape for ex-situ measurement.
  • Cu K-edge XANES spectra were recorded in fluorescence mode by continuously scanning the Si (11 1) monochromator (Quick XAS mode) from 8,880 to 9,020 eV, with 0.3 eV steps in the XANES region. All data were processed using the Lab VIEW custom BE 10.3.2 software to perform dead time correction, energy calibration, and glitch removal with detail procedure described elsewhere 14 XANES spectra were processed with Athena software 15 to find first derivative peak (3 ⁇ 4), pre-edge background substraetion and post-edge normalization, align and merge the spectra. EXAFS spectra were recorded up to 565 eV above the edge (8,880-9,545 eV, i.e , up to k ⁇ 12 A !
  • Copper-oxygen complexes are known to display unique spectroscopic properties that can distinguish one from another, particularly with combined UV-vis spectroscopy and resonance Raman spectroscopy.
  • From our UV-vis DRS spectroscopic data we observed the absorption bands centered at 400 nm and 650 nm. The absorption bands below 350 nm is indiscernible due to the overlapping with the absorption band of MOF-808.
  • OLEX2 a complete structure solution, refinement and analysis program. J Appl. Crystallogr. 42, 339-341 (2009).

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Abstract

Des catalyseurs à réseau de coordination organométallique (MOF) comprennent des ligands à base d'imidazole métalatés qui forment un complexe métal-oxygène réactif dans le MOF.
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CN112553186B (zh) * 2020-12-25 2023-08-18 华南理工大学 一种铜基金属有机框架材料固定化漆酶及其制备方法和应用
CN113262650A (zh) * 2021-04-23 2021-08-17 中国工程物理研究院材料研究所 用于氢同位素净化的二维mof膜及其制备方法和应用
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