Patent Application
20230191365
The invention relates to metal organic frameworks (MOFs) having a UTSA-16 structure. In particular, the invention relates to MOFs having good CO2 capture performance, and methods for making the MOFs that are significantly faster under milder reaction conditions.
The listing or discussion of a prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the state of the art or is common general knowledge.
Metal-organic frameworks (MOFs) are porous crystalline materials with a modular synthetic chemistry. Due to high compositional tuneability, they are amenable to precise materials engineering allowing excellent performance in numerous commercially interesting applications. For example, certain MOFs have exhibited large CO2 uptake capacities, high CO2 selectivity and prolonged stability making them excellent CO2 capture sorbents. The development of scalable and sustainable protocols is an essential step towards actual commercial applications of MOFs. This is because most intended MOF applications entail large footprints (e.g., ˜3000 tonnes sorbent for a capture unit integrated with a 500 MW coal-based power facility). As such, the environmental impact and cost of manufacture substantially affect the overall economic viability of the process.
UTSA-16 is a highly promising MOF material for CO2 capture by adsorption due to the isotherm features, mechanism of adsorption, and stability. Almost all reported syntheses for this material are based on the protocol in Journal of the American Chemical Society 2005, 127 (47), 16352-16353, where only the vessel and solvent volume are adjusted to meet the required scale of synthesis. The reported protocol involves mixing the precursor raw materials in 50%/50% ethanol-water mixed solvent, followed by isothermal heating for a fixed duration at 120° C., corresponding to autogenous pressures of 4 to 6 bar. Such solvothermal synthetic approach requires specialized reactors, introducing additional capital costs for production, and precludes the use of common glass equipment, where typical pressure rating is below 2 bar. Ongoing attempts to scale-up this material are hindered by failure to reduce the synthetic temperature below the boiling point of the solvent. In addition, the prevailing protocol also necessitates extended crystallization time (up to 2 days). The reaction efficiency, estimated in terms of space-time yield, is 25 kg (m3 day)* This needs to be increased by approximately ten-fold to be commercially viable. The ternary phase equilibria of deprotonated ligand salt in solution (i.e., tripotassium citrate+ethanol+water) involves a liquid-liquid phase separation. In the presence of cobalt salt, viscous gelation occurs. It is understood that mixing is detrimentally affected by high viscosity.
Transitioning from a closed-solvothermal condition to open-reflux synthesis with the usage of safe and cheap solvents is an important step towards scalable protocols. Reflux synthesis of MOFs leverages proven manufacturing process technologies and has been demonstrated in the production of an aluminium fumarate MOF at tonne-scale. The capital equipment cost, safety compliance cost and energy cost may all be reduced when a solvothermal process is replaced with a reflux synthetic process.
Reaction optimization of MOFs are highly system-specific. Most of the reported reflux synthetic protocols described for low-valence MOFs and for high-valence MOFs concern binary systems with a single metal precursor and single organic linker. These protocols do not accommodate the synthesis of materials having higher structural complexity. UTSA-16 possesses a unique chemical feature whereby metal species within distinct structural motifs exhibit different coordination geometries. The commonly accepted crystal-field theory predicts that one of these coordination geometries is significantly more favored in terms of stability. This has direct implications for synthesis, because conditions not conducive for the formation of the less stable motif will substantially compromise the kinetics and accordingly, the yield and efficiency of product formation.
There is therefore a need for improved materials and methods which can produce USTA-16 in a faster time under milder reactions, while retaining good CO2 capture performance.
It has been surprising found that incorporating a secondary metal component provides UTSA-16 analogues with improved CO2 capture performance that can be formed under significantly milder conditions and in a shorter time. This enables use of conventional laboratory equipment and open-reflux synthesis. The optimized protocols are more compatible with industrial production, paving the way for the mass production of these promising materials.
Aspects and embodiments of the current invention are listed in the following numbered clauses. 1. A metal organic framework (MOF) having a UTSA-16 structure, where the composition comprises:
It has been surprising found that incorporating a second metal as described herein provides mixed-metal UTSA-16 analogues that can be prepared under milder conditions relative to monometallic UTSA-16. These compounds possess an asymmetric site distribution of the first metal and second metal, and benefit from expanded reaction space and faster reaction kinetics. Additionally, the material disclosed herein may have improved gas separation properties and the underlying structure of UTSA-16 is maintained.
Thus, in a first aspect of the invention, there is provided a metal organic framework (MOF) having a UTSA-16 structure, where the composition comprises:
In embodiments herein, the word “comprising” may be interpreted as requiring the features mentioned, but not limiting the presence of other features. Alternatively, the word “comprising” may also relate to the situation where only the components/features listed are intended to be present (e.g. the word “comprising” may be replaced by the phrases “consists of” or “consists essentially of”). It is explicitly contemplated that both the broader and narrower interpretations can be applied to all aspects and embodiments of the present invention. In other words, the word “comprising” and synonyms thereof may be replaced by the phrase “consisting of” or the phrase “consists essentially of” or synonyms thereof and vice versa.
The phrase, “consists essentially of” and its pseudonyms may be interpreted herein to refer to a material where minor impurities may be present. For example, the material may be greater than or equal to 90% pure, such as greater than 95% pure, such as greater than 97% pure, such as greater than 99% pure, such as greater than 99.9% pure, such as greater than 99.99% pure, such as greater than 99.999% pure, such as 100% pure.
When used herein, the USTA-16 structure is taken to mean that the MOFs disclosed herein share a similar structure to that disclosed in the microporous cobalt citrate framework USTA-16 (University of Texas at San Antonio-16). However, for the avoidance of doubt, the compounds disclosed here use different constituent components.
As noted above, the first metal, when present, may be selected from one or more of the group consisting of Cr, Mn, Fe, Ni, Cu, and Co. For example, the first metal (when present) may be selected from one or both of Fe and Co or, more particularly, the first metal (when present) may be Co. As will be appreciated from the above, the first metal may or may not be present in the MOFs of the current invention. When the MOF is present, the first metal may represent up to 80 mol % of the total metal in the MOF. In particular embodiments of the invention when the first metal is present, it may represent from 25 to 50 mol % of the total metal present in the MOF.
As noted herein, the second metal may be selected from one or more of the group consisting of Cd, Mn, and Zn. In more particular embodiments that may be mentioned herein, the second metal may be Zn.
As will be appreciated, the second metal may be the only metal present in the MOF (i.e. the first metal represents 0 mol % and the second metal represents 100 mol % of the total metal in the MOF), but it may more typically be present in combination with the first metal. Thus, in embodiments of the invention, the second metal may represent from 20 to 80 mol %, such as from 25 to 100 mol %, such as from 50 to 75 mol % of the total metal in the MOF.
Thus, in embodiments of the invention, the MOF may contain:
(a) 0 mol % of the first metal and 100 mol % of the second metal;
(b) 25 mol % of the first metal and 75 mol % of the second metal;
(c) 50 mol % of the first metal and 50 mol % of the second metal;
(d) 75 mol % of the first metal and 25 mol % of the second metal; and
(e) 80 mol % of the first metal and 20 mol % of the second metal,
where 100 mol % represents the total metal in the MOF.
In microporous cobalt citrate framework USTA-16, there are tetrameric [Co4] clusters and monomeric [Co(O2CR)4] units, where the Co(II) species adopt octahedral and tetrahedral coordination environments, respectively.
In embodiments of the invention where only the second metal is present, then by analogy, the second metal will occupy both the octahedral and tetrahedral coordination environments. However, when the first metal is also present, the second metal will preferentially occupy tetrahedral metal sites within the MOF. For example, the majority of the second metal may occupy a tetrahedral metal site within the MOF. When used herein “majority” may mean 51 mol % of the second metal, such as 55 mol %, 60 mol % 70 mol, 75 mol %, 80 mol %, 85 mol %, 90 mol %, 95 mol %, or 99 mol % occupies the tetrahedral metal sites.
Similarly, when only a small amount of the second metal is present (e.g. 20 mol %), then the first metal may occupy both the octahedral and tetrahedral coordination environments. However, the first metal may display a preferential occupation of the octahedral metal sites. For example, the majority of the first metal, when present, may occupy an octahedral metal site within the MOF. When used herein “majority” may mean 51 mol % of the first metal, such as 55 mol %, 60 mol % 70 mol, 75 mol %, 80 mol %, 85 mol %, 90 mol %, 95 mol %, or 99 mol % occupies the octahedral metal sites.
Thus, in embodiments of the invention, where both the first and second metals are present, then the first metal and second metal preferentially occupy an octahedral metal site and a tetrahedral metal site within the MOF, respectively.
For example, when there is a 50:50 mixture of Zn and Co as the second and first metals, respectively, then 65 mol % of Zn may occupy the tetrahedral metal sites. Further, when there is a 25:75 mixture of Zn and Co as the second and first metals, respectively, then 82 mol % of Zn may occupy the tetrahedral metal sites.
The MOFs disclosed herein may have a specific surface area of from 300 to 1500 m2g−1, such as from 500 to 1000 m2g−1, such as from 691 to 863 m2g−1. The MOFs disclosed herein may be useful in CO2 capture. As such, the MOFs of the current invention may display a saturated CO2 uptake of up to 5.0 mmol/g, optionally wherein the MOF has a saturated CO2 uptake of from 2.5 to 4.5 mmol/g, such as from 3.39 to 3.50 mmol/g. Additionally or alternatively, the MOFs of the current invention may have a breakthrough CO2 working capacity of up to 2.2 mmol/g, such as from 1.0 to 1.8 mmol/g, such as from 1.65 to 1.70 mmol/g.
The MOFs disclosed herein may be conveniently prepared. As mentioned, the MOFs disclosed herein may be formed under milder conditions (such as lower temperature or pressure). Thus, in a second aspect of the invention, there is provided a method of forming a MOF as described herein, wherein the method comprises the step of aging a mixture comprising from a first metal precursor, a second metal precursor, a base, citric acid, a first solvent and a second solvent for a period of time at a temperature of from 15 to 200° C., wherein:
Any suitable temperature in the range of from 15 to 200° C. may be used. For example, the temperature may be from 20 to 150° C., such as from 40 to 120° C., such as temperature of from 60 to 80° C. In another embodiment, the temperature may be room temperature (that is, from 20 to 30° C., such as temperature of about 25° C.).
As noted above, the method makes use of a first and second solvent. As such, the temperature used in the preparation may result in one or both solvents being refluxed. The use of a reflux synthetic process as compared to a solvothermal process may reduce equipment cost, safety compliance cost and energy cost.
Any suitable solvents may be used as the first and second solvent. For example, the first solvent may be water and the second solvent may be an alkyl alcohol (e.g. the alkyl alcohol is methanol, a propanol or, more particularly, ethanol).
Any suitable base may be used in the method disclosed herein. For example, the base may be a metal hydroxide (e.g. the base is KOH). The method above may be performed under any suitable pressure. For example, the method may be performed under ambient atmospheric conditions (e.g. standard pressure). Again, this may reduce costs associated with the preparation of the MOF.
Any suitable chemical can be used as the first and second metal precursors. As will be appreciated, the chemicals selected will need to include the first and/or second metal to be able to act as a precursor. In embodiments of the invention that may be mentioned herein, the first and second metal precursors may be a metal salt, where the metal is in a cationic form, which is balanced by one or more counterions selected from one or more of halide (e.g. chloride), nitrate, sulfate, hydroxide, oxide, acetate anion, and hydrates thereof.
In particular embodiments that may be mentioned herein, the second metal precursor may be Zn(OAc)2 or a hydrate thereof (e.g. Zn(OAc)2·2H2O). Additionally or alternatively, the metal in the second metal precursor may be present in an amount of from 25 to 100 mol %, such as from 50 to 75 mol % of the total metal present in the mixture. In particular embodiments that may be mentioned herein, the first metal precursor is Fe(OAc)2, Co(OAc)2 or hydrates thereof (e.g. Co(OAc)2·4H2O). Additionally or alternatively, the metal in the first metal precursor may be present in an amount of from 25 to 50 mol %, such as from 50 to 75 mol %, such as from 25 to 50 mol % of the total metal present in the mixture.
As noted above, the MOF disclosed herein may be useful in capturing CO2. Thus, in a third aspect of the invention, there is provided a method of capturing CO2 comprising the step of exposing a material comprising a MOF as described herein to an environment containing CO2.
Further aspects and embodiments of the invention will now be described by reference to the following non-limiting examples.
Pristine UTSA-16(Co) contains tetrameric [Co4] clusters and monomeric [Co(O2CR)4] units coexisting in the framework, wherein Co∥ species adopt octahedral and tetrahedral coordination environments, respectively. In turn, these units form nodes with octahedral and trigonal connectivity, resulting in an anatase-type net. According to the crystal-field theory, the presence of weak-field ligands such as carboxylate and solvent molecules heavily prefers Co∥ in octahedral coordination. As a result, the low thermodynamic stability of tetrahedral Co∥ under the prevailing reaction conditions may reduce the driving force for the formation of the corresponding [Co(O2CR)4] motif, and in turn, kinetically limit the formation process of this material (
All the reagents were obtained from commercial sources and used without further purification. Ultrapure water was used as supplied from PU+ purification system (VWR).
Powder X-ray diffraction. For phase analysis, PXRD patterns with a 2θ range of 5-40° were collected on a Bruker D8 Advance instrument using Cu Kα radiation (λ=1.5418 Å). The data were collected at a scanning rate of 2°/min. The FWHM data derived for kinetic experiments were collected on a Rigaku Miniflex 600 diffractometer, also using Cu Kα radiation (λ=1.5418 Å). The patterns were collected from a 2θ range of 5-15° at a scanning rate of 2°/min.
ICP-OES. The metal compositions of mixed-metal UTSA-16 MOFs were analyzed by inductively coupled plasma optical emission spectrometry (ICP-OES, Optima 7300DV, Perkin Elmer). UTSA-16 samples were digested in 5% HNO3 aqueous solution, which allowed complete dissolution of the MOF. The solutions were transferred to low density polyethylene tubes (Fisher Scientific) for further tests.
FTIR-ATR spectroscopy. Fourier-transform infrared attenuated total reflectance (FTIR-ATR) spectra were recorded on a Bruker Vertex 70 spectrometer.
UV-Vis spectroscopy. Solid-state UV-Vis spectra were collected with a Shimadzu UV-2450 spectrophotometer in the range of 400-800 nm using BaSO4 as the standard.
XPS analysis. The photoelectron spectra (XPS) were collected using monochromatized Al Kα radiation (hv=1286.71 eV) at 15 kV on a Kratos Axis Ultra XPS system (Kratos Analytical). The measured binding energies (BEs) were referenced according to C 1 s peak (BE set at 284.5 eV) that corresponds to C-C bonds. The fit of Co high-resolution spectra considered individual peaks for the sites with octahedral coordination environment (Oh), the sites with tetrahedral coordination environment (Td), with the remaining contributions lumped into a single satellite signal. The fitting was performed simultaneously for the Co 2p3/2 and Co 2p1/2 orbitals after Shirley background subtraction. The peak full width at half maximum (FWHM) was constrained to be equivalent for either orbital, whereas the area ratios were constrained to be 2:1 according to spin-orbit splitting. A similar fitting was undertaken for the Zn 2p region but without the satellite contribution.
TGA experiments. Thermogravimetric analysis (TGA) data were collected using a Shimadzu DTG-60AH under an air flow of 30 mL/min. The samples were heated to 900° C. at a heating rate of 10° C./min.
EXAFS analysis. X-ray absorption fine structure (XAFS) spectra were collected in transmission mode at room temperature at the XAFCA beamline of the Singapore Synchrotron Light Source. The Co and Zn K-edge spectra were processed following the conventional procedure using the IFEFFIT package.
Synthetic and Activation Procedure
General Procedure 1. Solvothermal Synthesis of UTSA-16-Zn-x Materials
UTSA-16(Co) (or UTSA-16-Zn-0) was synthesized with reference to those reported in Journal of the American Chemical Society 2005, 127 (47), 16352-16353. Briefly, Co(OAc)2·4H2O (1 mmol), KOH (3 mmol), and citric acid (1 mmol) were mixed in H2O (2.5 mL) to yield a homogeneous aqueous solution. The solution was transferred into a Teflon-lined reaction vessel (15 mL). Next, absolute ethanol (2.5 mL) was introduced while manually stirring the vessel contents. To prepare the bimetallic UTSA-16-Zn-x materials, varying amounts of Co(OAc)2·4H2O were replaced by Zn(OAc)2·2H2O maintaining the overall stoichiometry of the metal precursor with respect to the ligand and KOH. The reaction mixtures were introduced into a preheated oven (Memmert UF) at 120° C., kept at that temperature for 2 days, and subsequently retrieved and cooled to room temperature. The protocols yield large single crystals (UTSA-16-Co) or powder which was recovered by centrifugation at 5000 rpm and washed with copious amounts of absolute methanol.
General Procedure 2. Growth of UTSA-16-Zn-x Single Crystals
UTSA-16-Zn-x single crystals can be grown at lower temperatures.
To grow UTSA-16-Zn-1.00 single crystals, 500 μL of 0.8 M Zn(OAc)2·2H2O solution in water was mixed with 500 μL of 0.8 M tripotassium citrate solution in water to yield a clear solution. Then 500 μL of 1 vol.% ethanol in water was added. The homogeneous reaction mixture was transferred to a loosely capped scintillation vial and incubated in a preheated oven at 80° C.
Crystals observable by optical microscope were recovered after approximately 24 h and kept in mother solution prior to SCXRD characterization.
To grow UTSA-16-Zn-0.25 single crystals, 375 μL of 0.8 M Co(OAc)2.4H2O solution in water was first mixed with 500 μL of 0.8 M tripotassium citrate solution in water. Next, 125 μL of 0.8 M Zn(OAc)2·2H2O solution in water and 500 μL of 1 vol.% ethanol in water were sequentially added. The same heating and storage protocols were used as UTSA-16-Zn-1.00 (ICP result: 63.3% Co and 36.7% Zn).
It is noted that the single crystal recipe involves an open system where solvent is lost through evaporation. Hence the measured Co/Zn composition may reasonably differ from the feed and differ for different synthetic conditions. In all cases, however, strong preferential occupancy of sites was observed.
General Procedure 3. Activation of UTSA-16-Zn-x Mterials
Powder samples were exchanged with fresh methanol daily to dissolve excess ligand or metal precursors. The samples were dried under dynamic vacuum at room temperature for 24 h to yield dry solid products. All samples tested in adsorption measurements were activated (see Examples 6 and 7). For characterization, samples were activated beforehand but may be exposed to environment or solvent in the course of the characterization.
Mixed-metal MOF samples containing Co and Zn—denoted as UTSA-16-Zn-x, where x represents the feed molar fraction of Zn in the mixed Zn/Co precursors, and x=0, 0.25, 0.50, 0.75 or 1.00—were prepared by a one-pot synthetic method in accordance with General Procedure 1.
Bulk-phase characterization confirms that all of the samples have the same phase. Powder X-ray diffraction (PXRD) measurements confirm a sole crystalline phase identical to that of UTSA-16 (
In line with the changing sample colour (
The site occupancies within the bulk mixed-metal MOFs were assessed by measuring room temperature extended X-ray absorption fine structure (EXAFS) spectra of mixed-metal samples with varying Zn loadings (x=0, 0.25, 0.50, 0.75, 1.00) at the Co and Zn K-edges. X-ray absorption near edge structure (XANES) spectra (
The BET method was used to determine the specific surface areas of the UTSA-16-Zn-x materials. Adsorption data were collected at 77 K. The obtained specific surface areas are listed below in Table 3.
The asymmetric site distribution of Co and Zn within UTSA-16-Zn-x is proven using X-ray absorption spectroscopy.
Fourier-transformed EXAFS data at the Co and Zn K-edge for all the MOF samples are shown in
Quantitation of the site distribution based on EXAFS data was performed by simultaneous fitting of Co and Zn K-edges of the mixed-metal samples according to the previous treatment of metal site doping in oxide materials (Physical Review B 2002, 66 (22), 224405). The path amplitudes were parameterized using the fraction of either metallic species occupying the tetrahedral sites, YCo,tet and YZn,tet. The amplitude parameters were referenced to the monometallic Co and Zn samples, for which the site occupancy has been established prior by SCXRD (Journal of the American Chemical Society 2005, 127 (47), 16352-16353). Other parameters are defined as described below. Results of the combined EXAFS fitting of eight independent data sets are shown in
The reported and collected crystal data for UTSA-16 (Co) and UTSA-16 (Zn) were imported and the relevant scattering paths were generated using the FEFF programme. Paths with length below 2.5 Å were considered for the fitting. Four path parameters, S02, E0, ΔR, and σ2 are considered for each path. The path degeneracy, N, was kept as specified by the FEFF software.
A single global E0 was specified as a refinable parameter for each edge.
In the monometallic samples, i.e. x=0 and x=1, S02 is parameterized as a single refinable parameter. The contribution for the Cotet—O and Cooct—O single scattering paths were weighted by 0.33 and 0.67 respectively, according to their stoichiometry within the solved crystal structure. For UTSA-16-Zn-x (x=1), an analogous weighting scheme was specified. In the bimetallic samples, the distribution between octahedral and tetrahedral sites in the structure was parameterized as YCo,tet (x=0.25), YZn,tet (x=0.25), etc. and introduced as a weighting factor. These were then referenced to S0t of the monometallic samples. In other words, S02 of the Cotet—O scatterer in x=0.25 is defined as (S02, x=0×YCo,tet (x=0.25)), whereas S02 of the Cooct—O scatterer is [S02, x=0×(1−YCo,tet (x=0.25))].
ΔR is parameterized as a single refinable parameter for each edge, weighted by the respective Reff of each path.
The Debye-Waller factors of Cotet—O, Cooct—O, Zntet—O, Znoct—O were reasonably expected to differ, and a single refinable parameter was defined for each.
All the parameters were freely varied during the simultaneous fit of all the eight datasets, resulting in the calculation of the global R-factor.
Fitted ΔR and σ2 converge to physically reasonable values, which are summarized below. Note that the amplitude reduction factor (S02) is slightly above the typical range (0.7-1.1) for both edges.
The further possibility of determining site occupancy by SCXRD arises due to the three-electron difference between Co and Zn incorporated in the samples. To prepare samples of suitable size for the data collection of SCXRD, a modified protocol was adopted. Specifically, large single crystals of UTSA-16-Zn-1.00 and UTSA-16-Zn-0.25 were grown according to General Procedure 2.
The unconstrained refinement of occupancy factors in the octahedral and tetrahedral sites indicates near full occupation of the tetrahedral site by Zn, whereas the Zn occupancy in the octahedral site is approximately 20% for UTSA-16-Zn-0.25. This model agrees well with the diffraction data (see Table 6). The regressed occupancies correspond to a bulk composition of 68.3% Co and 31.7% Zn within the single crystal (ICP result: 63.3% Co and 36.7% Zn).
Single-Crystal X-Ray Diffraction (SCXRD)
Single-crystal X-ray diffraction data of UTSA-16-Zn-1.00 and UTSA-16-Zn-0.25were collected at 100 K on a Bruker D8 Venture diffractometer. The data integration and reduction were processed with SAINT software. A multi-scan absorption correction was applied to the collected reflections. The structure was solved by the direct method using SHELXTL and was refined on F2 by full-matrix least-squares technique using the SHELXL-2014/7 package within the WINGX programme. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were located in successive difference Fourier maps and they were treated as riding atoms using SHELXL default parameters. The structures were examined using the Adsym subroutine of PLATON to assure that no additional symmetry could be applied to the models.
Temperature-dependent crystalization of UTSA-16(Co) (viz. UTSA-16-Zn-0) and UTSA-16-Zn-0.50 were compared.
Temperature-Dependent Crystallization
The reaction mixtures (corresponding to UTSA-16-Zn-0 and UTSA-16-Zn-0.50) were prepared in accordance with General Procedure 1 except that the heating was done for 24 h in preheated ovens at the defined temperatures (60, 80, 100° C.), or at room temperature (25° C.).
The samples were recovered by centrifugation at 5000 rpm, washed with copious amounts of absolute MeOH before being dried in a vacuum oven for PXRD tests. Due to significant Co content in the samples, the samples exhibited high signal-to-noise ratio owing to X-ray absorption when using Cu Kα radiation source (Rigaku Miniflex). Hence, the samples were background-subtracted and filtered by Savitsky-Golay function using instrument-accompanying processing software (Rigaku PDXL). The same processing method was performed for all samples in
Results
In the case of the monometallic parent MOF (UTSA-16-Zn-0), a sticky gel was deposited from which violet prismatic crystals emerged. XRD patterns collected on products crystallized from incubation for 24 h at 25, 60, 80, and 100° C. (
The effect of Zn loading on the formation kinetics was estimated by ex-situ PXRD studies. The MOF formation kinetics was estimated by the inverse of the full-width at half-maximum (FWHM) of the dominant PXRD peak at ca. 7.5°, which was further normalized by the long-time average for comparability across different Zn loadings.
Method
For accurate estimation of induction time, the composition was optimized to ensure a homogenous starting solution. In light of salting-out effects, it is necessary to balance the solvent composition to suppress liquid-liquid phase separation. Here, a starting solution of M∥(acetate)-K3(citrate) (0.4 M in 15 vol % aqueous EtOH solution) was used.
The final composition of a 10 mL solution comprises 1.5 mL EtOH, 8.5 mL H2O, 4 mmol of M∥(acetate), and 4 mmol of citric acid neutralized with 12 mmol KOH. The 4 mmol of M∥(acetate) will be further apportioned into the two metals, keeping all other reagent quantities constant. For example, a 50/50 solution (x=0.5) may be prepared with 2 mmol of Co(OAc)2·4H2O and 2 mmol of Zn(OAc)2·2H2O with 4 mmol of citric acid neutralized with 12 mmol KOH in 5 mL H2O as solvent. Then, 1.5 mL EtOH+3.5 mL H2O solution is added to start the experiment. Different relative amounts of Co/Zn can be prepared by varying the relative ratio of M∥(acetate) without changing the total molar amount. For example, 25/75 (x=0.75) and 75/25 (x=0.25) mixtures can be prepared using 1 mmol of Co(OAc)2·4H2O and 3 mmol of Zn(OAc)2·2H2O or 3 mmol of Co(OAc)2·4H2O and 1 mmol of Zn(OAc)2·2H2O, respectively. The concentration of EtOH is strongly correlated with solid precipitation; to avoid immediate formation of solid, EtOH was added as a dilute solution (<30%) in water. The samples were incubated in a preheated oven at 65° C., removed at fixed intervals and ice quenched. The products were centrifuged (8,000 rpm for 3 min), dried under vacuum at room temperature, and subject to PXRD measurements. The time for products recovery was minimized and kept constant between samples with different Zn loadings. For samples with no solid isolated after the centrifugation, the FWHM is reported as 0.
Results
Even a modest Zn loading (x=0.25) can greatly reduce the induction time to around 70 min These results inform a certain feasibility to obtain mixed-metal UTSA-16 materials at ambient pressure within reasonable synthetic durations (<48 h).
In
Gas Sorption Experiments
The gas isotherms were measured up to 1 bar using a Micromeritics ASAP 2020 surface area and pore size analyzer. Before the measurements, the samples were degassed under reduced pressure (<10−2 Pa) at 150° C. until the outgas rate was below 5 μm Hg/min. UHP grade N2 and CO2 were used for gas sorption measurements. Oil-free vacuum pumps and oil-free pressure regulators were used to prevent contamination of the samples during the degassing process and isotherm measurement. The temperatures of 77, 273, and 298 K were maintained with a liquid nitrogen bath, an ice water bath, and under room temperature, respectively.
Fitting of CO2 Isotherms
Measured CO2 isotherms were fitted using the dual-site Langmuir Freundlich (DSLF) isotherm model,
The model accounts for site inhomogeneity by defining two adsorption sites A and B with distinct saturation capacities and affinity parameters.
Here, q is the amount of adsorbed gas, qsat is the amount of gas adsorbed at saturation (mmol g−1), b is the Langmuir-Freundlich affinity parameter (kPa−1), and a is a dimensionless exponent.
The simultaneous fitting at 298 K and 273 K was performed by inbuilt Solver function in Microsoft Excel, where the temperature dependence is described by independent b terms.
Fitting of N2 Isotherms
Measured N2 isotherms were fitted using the single-site Langmuir (SSL) isotherm model,
Due to low curvature of the isotherms, independent fitting for samples with different Zn loadings led to large variance in the obtained parameters. To reduce the number of free parameters, the qsat values of the individual UTSA-16-Zn-x sample were restrained to a common value scaled by their N2 uptake at 100 kPa. This restraint is supported by the substantial agreement of the isotherms, their isostructural nature, and very similar adsorption behaviour with respect to CO2.
Results
Single component CO2 and N2 isotherms were collected for UTSA-16-Zn-x at 273 and 298 K. The shape of CO2 isotherms and total uptake of CO2 at 1 bar are substantially similar to that of the parent Co one. In addition, several other parameters obtained by analysing the isotherms, such as isosteric heat of CO2 adsorption (Qst) and CO2/N2 selectivity calculated by ideal adsorbed solution theory (IAST) are also identical (
Breakthrough experiments were also performed using simulated flue gas (15/85 002/N2 feed) to analyze competitive adsorption under dynamic conditions.
Breakthrough Experiments
The breakthrough experiments were conducted using a home-built setup shown in
The feed flow rates during the experiment were controlled using mass flow controllers (error: 0.1 sccm). The total flow rate through the column was set to 3 sccm. These were stabilized using a bypass line and switched to flow through the adsorbent column immediately prior to the experiment.
The gas composition at the exit of the column was determined by a mass spectrometer (Hiden QGA). To precisely determine the flow rates, Ar was introduced at a fixed flow rate of 3 sccm to the effluent gas as an internal reference to calibrate the mass flow rate. The upstream and downstream pressures were recorded. The original breakthrough plots were obtained as relative compositions vs. elapsed time and then converted to mole fraction normalized with the mole fraction at the inlet vs. elapsed time plots.
The performance evaluation is based on 3 experiments:
Dry Feed (RH=0%)—
The column was activated by purging a constant He flow of 10 sccm through the column at 120° C. for 24 h. The feed gas was a (15±1)/(85±1) CO2/N2 mixture prepared by mixing dry gas upstream of the column.
Wet Feed (RH=85%)—
The column was activated by purging a constant He flow of 10 sccm through the column at 120° C. for 24 h. The feed gas was a (15±1)/(85±1) CO2/N2 mixture with relative humidity of around 85%; the moisture was introduced by passing the N2 stream through a water bubbler at room temperature prior to mixing.
Water-Saturated Sorbent Bed (Sat. Col.)—
The column was activated by purging a constant He flow of 10 sccm through the column at 120° C. for 24 h. For pre-saturation, a wet purge stream was prepared by passing a N2 stream through a water bubbler at room temperature prior to mixing. The purge stream was sent through the column for 72 h until a stable water signal was detected by the mass spectrometer. Then, the column was briefly activated under constant He flow (10 sccm) at room temperature. This condition has been observed by us to enable near complete desorption of N2/002 but minimal desorption of adsorbed H2O. The experiment was then performed using ‘wet feed’ conditions. Under these conditions, the MOF-packed columns showed negligible uptake for either component.
The mean residence time within the adsorption column was obtained by performing a mass balance using the inlet and exit gas molar flow rates, i.e.
The obtained residence time was corrected by the residence time of a control experiment using a blank tube under the same pressure drop and feed conditions. The validity of this correction depends on a linear additive relationship for retention time and band broadening characteristics of the experiment. Uncorrected breakthrough curves (
Results
The saturated CO2 uptakes of UTSA-16-Zn-x are in the range of 1.65-1.70 mmol g−1 with substantial tolerance to moisture (
The maximum productivity of CO2 (qmax) is in good agreement with the single-component static uptake (1.8 mmol g−1 and 1.94 mmol g−1 respectively for x=0.5 and 1). In general, there is a slightly lower capacity (−2.3%) when transiting from dry to RH=85% feed, due to competitive adsorption by H2O.
CO2
In summary, we have shown that the replacement of rate-limiting tetrahedral Co species within UTSA-1 6 by Zn can dramatically accelerate the formation kinetics of these MOFs, affording mild synthetic conditions suitable for the mass production of those materials. The new UTSA-16-type MOFs exhibit CO2 capture performance identical to that of the parent Co one, with substantial tolerance to moisture.
The invention yields mixed-metal composites from a known binary (single metal/single linker) MOF with suitable structure, which possess improved synthetic robustness compared to the monometallic materials. Optimized protocols derived from this strategy are more compatible with scaled-up production, which will accelerate the process development of the concerned materials for various commercial applications.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10202004387T | May 2020 | SG | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/SG2021/050222 | 4/19/2021 | WO |
