Synthesis Process for Solid Carbon Capture Materials

Abstract

A method for forming an amine-functionalized solid CO.sub.2 sorbent for carbon capture may include providing a support material and applying at least one cycle of molecular layer deposition (MLD) with an amine precursor onto the surface of the support material. An amine layer formed on the support material contains amine groups/amine-containing ligands to adsorb CO.sub.2 onto the support material in a low temperature operating window for adsorption and desorption without the loss of active sites.

Claims

1. A method of forming an amine-functionalized solid CO.sub.2 sorbent comprising: providing a support material; and applying an amine layer onto at least a portion of a surface of the support material by performing at least one cycle of molecular layer deposition (MLD) with a first precursor and a second precursor, wherein the first precursor comprises an amine precursor.

2. The method of claim 1, wherein the first precursor comprises an aminopropyl-silane.

3. The method of claim 2, wherein the first precursor comprises aminopropyltriethoxysilane (mono-amine or APTS), N.sup.1-(3-trimethoxysilylpropyl) diethylene triamine (tri-amine), and/or N-[3-(trimethoxysilyl) propyl] ethylenediamine (di-amine).

4. The method of claim 1, wherein the second precursor comprises water.

5. The method of claim 1, wherein between the first precursor and the second precursor the surface of the support material is purged with nitrogen gas.

6. The method of claim 1, wherein the support material comprises a silica-based support material, the silica-based support material comprising fumed silica, silica fume, porous silica, mesoporous silica, silica gel, silica aerogel, silica nanotubes, and/or silica foam.

7. The method of claim 1, wherein the support material comprises alumina, titanium, zirconia, metal-organic frameworks, polymers, carbon nanotubes/fibers, zeolites, carbon black, carbon particles and/or activated carbon.

8. The method of claim 1, wherein at least 5 cycles of MLD are performed.

9. The method of claim 1, wherein at least 10 cycles of MLD are performed.

10. The method of claim 1, the support material comprises a nano-powder.

11. An amine-functionalized solid CO.sub.2 sorbent comprising: a support material; an amine layer; and wherein the amine layer forms chemical bonds to the support material.

12. The amine-functionalized solid CO.sub.2 sorbent of claim 11, wherein the amine layer has a thickness corresponding to at least one cycle of molecular layer deposition (MLD) with a first precursor and a second precursor.

13. The amine-functionalized solid CO.sub.2 sorbent of claim 12, wherein the thickness of the amine layer corresponds to at least five cycles of MLD.

14. The amine-functionalized solid CO.sub.2 sorbent of claim 12, wherein the support material is a porous material, and a total surface area of the support material is coated with the amine layer.

15. The amine-functionalized solid CO.sub.2 sorbent of claim 12, wherein the support material comprises a nano-powder.

16. The amine-functionalized solid CO.sub.2 sorbent of claim 12, wherein the first precursor comprises an aminopropyl-silane.

17. The amine-functionalized solid CO.sub.2 sorbent of claim 16, wherein the first precursor comprises aminopropyltriethoxysilane (mono-amine or APTS), N.sup.1-(3-trimethoxysilylpropyl) diethylene triamine (tri-amine), and/or N-[3-(trimethoxysilyl) propyl] ethylenediamine (di-amine).

18. The amine-functionalized solid CO.sub.2 sorbent of claim 12, wherein the second precursor comprises water.

19. The amine-functionalized solid CO.sub.2 sorbent of claim 11, wherein the support material comprises a silica-based support material, the silica-based support material comprising fumed silica, silica fume, porous silica, mesoporous silica, silica gel, silica aerogel, silica nanotubes, and/or silica foam.

20. The amine-functionalized solid CO.sub.2 sorbent of claim 11, wherein the support material comprises alumina, titanium, zirconia, metal-organic frameworks, polymers, carbon nanotubes/fibers, zeolites, carbon black, carbon particles and/or activated carbon.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] FIG. 1 shows a schematic flow chart of a method of forming an improved amine-functionalized, solid CO.sub.2 sorbent according to an embodiment of the disclosure.

[0028] FIG. 2 shows a chemical reaction diagram of a method of forming an improved amine-functionalized, solid CO.sub.2 sorbent according to an embodiment of the disclosure

[0029] FIG. 3 is a simplified, schematic cross-sectional view of an improved amine-functionalized, solid CO.sub.2 sorbent according to an embodiment of the disclosure.

[0030] FIG. 4 shows chemical structures of aminopropyl-silane molecules aminopropyltriethoxysilane (mono-amine or APTS), N.sup.1-(3-trimethoxysilylpropyl) diethylene triamine (tri-amine), and N-[3-(trimethoxysilyl) propyl] ethylenediamine (di-amine).

[0031] FIG. 5 is a schematic plan view of an MLD fluidized bed reactor system according to an embodiment of the disclosure.

[0032] FIG. 6 shows the results of a simplified mass spectrometry trace for a single cycle of mono-amine MLD according to an embodiment of the disclosure.

[0033] FIG. 7 shows the results of a simplified mass spectrometry trace for a single cycle of tri-amine MLD according to an embodiment of the disclosure.

[0034] FIG. 8 shows nitrogen content in weight percent versus a mono-amine/water MLD cycle number according to an embodiment of the disclosure.

[0035] FIG. 9 shows a comparison of the nitrogen content of a functionalized substrate after 10 MLD cycles with mono-amine versus the nitrogen content of a functionalized substrate after 10 MLD cycles with tri-amine, according to some embodiments of the disclosure.

[0036] FIG. 10 shows the results of thermogravimetric analysis for thermal cycling between CO.sub.2 adsorption and desorption temperatures for 25 cycles of a functionalized substrate after 10 MLD cycles with mono-amine versus a functionalized substrate after 10 MLD cycles with tri-amine, according to some embodiments of the disclosure.

[0037] FIG. 11 shows the results of Quantachrome Gas Sorption Analyzer CO.sub.2 monolayer uptake measurements for uncoated (before undergoing MLD functionalization), 5-cycle, and 10-cycle samples of a mono-amine functionalized substrate according to some embodiments of the disclosure.

[0038] FIG. 12 shows thermogravimetric analysis curves of weight % of sorbent sample vs. time at transition from inert environment to CO.sub.2 introduction for a functionalized substrate after 10 MLD cycles with mono-amine, a functionalized substrate after 10 MLD cycles with tri-amine, and a functionalized substrate after 15 MLD cycles with tri-amine, according to some embodiments of the disclosure.

[0039] FIG. 13 shows calculated CO.sub.2 adsorption capacities for uncoated, 5-cycle, and 10-cycle samples of a mono-amine functionalized substrate according to the embodiments of FIG. 12.

[0040] The drawings and figures are not necessarily drawn to scale, unless otherwise indicated, but instead are drawn to provide a better understanding of the components, and are not intended to be limiting in scope, but to provide exemplary illustrations.

DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS

[0041] To further clarify the above and other advantages and features of the present disclosure, a more particular description will be rendered by reference to specific embodiments thereof, which are illustrated in the appended drawings. It is appreciated that these drawings depict only typical embodiments of the disclosure and are therefore not to be considered limiting of its scope. The present disclosure will be described and explained with additional specificity and detail through the use of the accompanying drawings, in which like reference characters refer to like elements.

[0042] It is to be understood that disclosure is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments and is not intended to be limiting in any way.

[0043] Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the disclosure. Also, unless expressly stated to the contrary: description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.

[0044] It must also be noted that, as used in the specification and the appended claims, the singular form “a,” “an,” and “the” may comprise plural references unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.

[0045] The terms “substrate,” “support material,” and the like are used interchangeably in the specification and may be commonly understood as a carrier material having a surface area available for functionalization.

[0046] As discussed above, existing functionalization methods suffer from high costs, a limited range of effective substrate materials, and complex and sensitive manufacturing processes. Conventional solid CO.sub.2 sorbents may provide only limited functionalization of available surface area and/or suffer the loss of amine active sites during regeneration. Embodiments of the present disclosure provide an improved amine-functionalized, solid CO.sub.2 sorbent that offers a proven reduction in energy requirements for regeneration of active sites while increasing durability and long-term stability at a lower cost than conventional solid sorbents. The advantages, including regenerative, durability and cost saving properties, of the disclosed amine-functionalized, solid CO.sub.2 sorbent may be due to the preparation methods used, and embodiments of the disclosure include methods for forming the disclosed amine-functionalized, solid CO.sub.2 sorbent, including related methods of use.

[0047] Referring now to FIG. 1, a method 100 of forming an improved amine-functionalized, solid CO.sub.2 sorbent according to an embodiment of the disclosure is shown schematically in a flow chart. The method 100 may include providing a support material at step 110. The support material may be a conventional amine support material or another support material. According to various embodiments, the support material may comprise silica-based support materials, such as fumed silica, silica fume, porous and mesoporous silica, silica gel, silica aerogel, silica nanotubes, and silica foam, or may comprise alumina, titanium, zirconia, metal-organic frameworks, polymers, carbon nanotubes/fibers, zeolites, carbon black, carbon particles and/or activated carbon. In embodiments, the support material may be provided in a powdered form, such as in the form of a nano-powder or nano-powder agglomerate.

[0048] The method 100 may include the step 120 of applying an amine layer onto at least a portion of a surface of the support material. In various embodiments of the disclosure, the application of the amine layer onto at least the portion of the surface of the support material may be performed by one or more cycles, or surface reaction steps, of MLD or ALD.

[0049] In one embodiment, active sites may be added to the support material using a first precursor and a second precursor as alternating reagents, for example in a fluidized bed reactor 500 as illustrated in FIG. 5 or using a similar system or device. In the example of a fluidized bed reactor, the first and the second precursor may be passed through the solid support material at high speeds in order fluidize, or suspend and cause to behave as a fluid, the solid support material. When fluidizing the solid support material, the fluidization can be assisted by mechanical vibration, pulsing of the gas, by adding downward facing micro-nozzles above the distributor to produce microjets at very high velocity, or by another means as would be understood by one skilled in the art from the present disclosure.

[0050] In methods of the disclosure, a first precursor and a second precursor dose may be applied as sequential half-cycles in a single MLD cycle. The reactor may be purged between half-cycles, such as with nitrogen gas (N2) or an inert gas, with the first precursor and the second precursor acting as alternating reagents. The first precursor and the second precursor may be applied separately at a reactor bed temperature between 130° C. to 170° C., or at least 130° C.

[0051] The first precursor may comprise an amine precursor, such as aminopropyl-silane molecules, and the second precursor may include water. Aminopropyl-silane molecules comprise at least aminopropyltriethoxysilane (mono-amine or APTS), N.sup.1-(3-trimethoxysilylpropyl) diethylene triamine, or tri-amine, and N-[3-(trimethoxysilyl) propyl] ethylenediamine, or di-amine, as shown in FIG. 4. Additional amine precursors may be employed in the method, as would be understood from the current disclosure by one skilled in the art.

[0052] The use of MLD for applying the amine layer advantageously allows for angstrom-level thickness control over the growth on the support material and the amine layer may be formed homogenously on the support material such that amine active sites are present evenly across the surface of the support material with the amine layer. In like manner, the use of gas-phase precursors in the described methods may advantageously allow for a complete saturation or coating of the support material with an amine layer, even in porous and very small particles.

[0053] Methods of the instant disclosure allow for increased control in the application of amine active sites to the substrate and corresponding fine-tuning of the sorbent properties relative to prior art methods. The controlled application of the amine layer by at least 1 cycle of MLD, at least 5 cycles, at least 10 cycles, at least 15 cycles, or at least 20 cycles, allows for precise control of the thickness of the amine layer and resulting amine active sites in the CO.sub.2 sorbent. As would be recognized by one skilled in the art from the present disclosure, the step 120 of applying an amine layer onto at least a portion of a surface of the support material may include a plurality of MLD cycles or may include a single cycle where the step 120 may be repeated to achieve a desired thickness of the amine layer.

[0054] According to an embodiment of the method, application of an amine layer may be exemplified by the chemical reaction diagram illustrated in FIG. 2. In the method 200, a silica-based support material 210 may be provided including hydroxyl groups 212 on a silica surface. Aminosilane molecules 220 may be introduced to the silica surface as the first precursor, where reactions occur between the aminosilane molecule 220 and the hydroxyl groups 212, forming ethanol or methanol as a byproduct depending on the alkoyy group (R) present on the aminosilane.

[0055] Introduction of water as the second precursor causes a reaction between the water and alkoxy groups 222 of the deposited amine molecule 220 to produce ethanol or methanol as a leaving group and produces additional hydroxyl groups to react with the first precursor in a subsequent cycle.

[0056] In a resulting 1-cycle amine functionalized solid sorbent 230, the aminopropyltriethoxysilane molecules 220 are covalently bonded to the silica surface and provide amine active sites for adsorption and hydroxyl groups for the introduction of another MLD cycle of aminosilane molecules and water, such as for forming a 1.5-cycle amine functionalized solid sorbent 240.

[0057] As would be recognized from the amine-functionalized solid sorbents illustrated in FIG. 2, methods of the present disclosure provide an improved functionalization of the support material with an amine layer that is covalently bonded and includes a greater number of active sites for carbon capture relative to conventional functionalization methods.

[0058] According to differing embodiments, the amine of the first precursor may be maintained from one cycle of MLD to the next or the amine of the first precursor may be changed between cycles for the formation of different alkylamine networks. In an example of the methods of the disclosure, a uniform monolayer film of amine active sites may be formed on the substrate material. The amine layer may form a continuous film coating the entirety of a substrate surface, which may be particularly advantageous when used with a porous substrate for increasing surface area available for chemisorption of CO.sub.2, or may be controlled to form a discontinuous film on predetermined areas of the support material.

[0059] Similarly, the self-limiting nature of the reaction steps of the method allow for a precise control of the amine layer thickness, such that the thickness of the amine layer may be increased to maximize adsorption capacity. In an example, the surface area of the support material may be completely saturated with amines, such that steric hindrance prevents the introduction of additional amines. Similarly, the method may be precisely controlled to maximize adsorption capacity of the support material without diminishing returns that may result from over-application of the amine layer, such as by filling pores in the support material that may reduce adsorption due to diffusion limitations.

[0060] As shown in the simplified, schematic cross-sectional view of FIG. 3, an embodiment of the current disclosure includes an amine-functionalized solid CO.sub.2 sorbent, such as formed by methods of the current disclosure. The sorbent 300 includes a support material 310 and an amine layer 330 overlying the support material 310, as schematically illustrated in FIG. 3. While shown in simplified form in FIG. 3, the support material 310 may include particles, porous materials, and may be configured with any suitable shape or size for use in carbon capture applications and methods. In like manner, the amine layer 330 may be formed as a continuous and/or uniform film and may be arranged to completely coat any exposed surface area of the support material 310, including within pores of the support material 310. In alternative embodiments, the amine layer 330 may be applied as a discontinuous film on the support material 310 or as a film on predetermined portions of the support material 310.

[0061] The support material 310 may include silica-based support materials, such as fumed silica, silica fume, porous and mesoporous silica, silica gel, silica aerogel, silica nanotubes, and silica foam, or may include alumina, titanium, zirconia, metal-organic frameworks, polymers, carbon nanotubes/fibers, zeolites, carbon black, carbon particles and/or activated carbon. The support material may be provided in the form of a porous substrate and/or in the form of substrate particles, the substrate presenting either a substantially uniform or non-uniform surface area for receiving an amine layer in the form of amine groups deposited on the support material as a CO.sub.2 adsorption material.

[0062] According to varying embodiments, the support material may be a chemically unmodified or commonly available substrate material. In one example, the support material may comprise fumed silica or silica fume as is widely available commercially at a very low cost much less than the cost of specialized substrates, for example silica aerogel. The use of common silica materials dramatically reduces the cost of amine-functionalized solid CO.sub.2 sorbents of the present application relative to conventional solid CO.sub.2 sorbents, and the methods and products according to the disclosed embodiments can therefore be far more commercially viable than existing solid CO.sub.2 sorbents that require specialized substrates, costly preparation methods, and complicated manufacturing processes.

[0063] The support material may comprise a nano-powder material having an individual particle size in the range of 1 nm to 100 nm, in another example having an individual particle size in the range of 1 nm to 20 nm. The use of nano-powders as support materials advantageously results in an enormous increase in functionalized surface area relative to larger particles used in conventional sorbents. When fluidized, nano-powders may form large agglomerates on the order of 100 μm which are extremely porous. While individual nanoparticles cannot be fluidized, ALD and MLD methods are able to coat the surface of each individual nanoparticle in the fluidized porous agglomerates. While particles of such a small size have not previously been successfully adapted for use in solid CO.sub.2 sorbents, or at least not in a commercially viable and operationally effective manner, the methods of the current application have realized a simple functionalization of nano-powder substrates that is able to saturate the surface of said nano-powders or nano-powder agglomerates with amines.

[0064] In one example, the support material may comprise a silica-based nano-powder. Silica nano-powders have the benefit of an incredibly high surface area due to the large area/volume ratio of the material. The larger the surface area of the particles, the greater the number of hydroxyl groups present for functionalization. Methods of the present disclosure present the further benefit of precisely controlled, gas-phase deposition, advantageously enabling functionalization of a greater surface area of the support material than may be achieve in conventional methods.

[0065] In embodiments, a surface of the support material 310 may be completely saturated with amine groups of the amine layer 330. The functionalized solid sorbent may include a surface area of the support material coated with the amine layer, said surface area defined by an exterior surface of the support material and an interior surface of pores formed within the support material. According to varying embodiments, the amine layer may form a continuous and/or uniform film on the support layer or on the surface area of the support material.

[0066] In varying examples, the amine-functionalized solid CO.sub.2 sorbent may include a nitrogen weight percent of at least 1.00%, at least 1.25%, or preferably at least 1.40%, the nitrogen content being proportional to the number of amine groups in the amine layer 330.

[0067] The amine-functionalized solid CO.sub.2 sorbent may be configured with an adsorption capacity of at least 1.00 mmol CO.sub.2/g sorbent, at least 1.50 mmol CO.sub.2/g sorbent, at least 1.80 mmol CO.sub.2/g sorbent, at least 2.00 mmol CO.sub.2/g sorbent, at least 2.50 mmol CO.sub.2/g sorbent, or at least 3.00 mmol CO.sub.2/g sorbent. No similar adsorption capacity has been previously realized using MLD produced solid CO.sub.2 sorbents, and especially not using nano-powder support materials.

[0068] Surprisingly, it has been discovered that amine-functionalized solid CO.sub.2 sorbents according to the present disclosure have the ability to regenerate amine active sites through cycles of adsorption and desorption without any noticeable depletion in amine groups. Accordingly, the amine-functionalized solid CO.sub.2 sorbents have an increased durability and useful life relative to conventional solid sorbents, allowing the advantage of low energy regeneration in industrial use without the increased costs associated with replacing depleted conventional sorbents.

EXPERIMENTAL EXAMPLES

[0069] The following experimental examples are provided to illustrate an embodiment of the current disclosure and to more particularly demonstrate the advantages of the embodiments but are not intended to limit the scope thereof.

[0070] In experimental examples according to some embodiments of the method, samples of various cycle numbers, using MLD of both mono- and tri-amine molecules, were synthesized. FIG. 5 provides a schematic of a stainless-steel fluidized bed reactor (FBR) system that may be used in sorbent synthesis. Related systems and devices may be employed for the disclosed methods, as would be understood by one of ordinary skill in the art from the instant description. MLD of each amine precursor molecule was carried out separately with water at a reactor bed temperature of 150° C. and an amine bubbler temperature of 90° C. The amine molecule and water acted as alternating reagents.

[0071] One MLD cycle of each chemistry included the sequential exposure of the aminopropyl-silane molecule and water with inert nitrogen purges in-between. CAB-O-SIL untreated fumed silica (SiO.sub.2) from Cabot was used as the substrate. About 3 grams of fumed (nano) SiO.sub.2 was loaded into the MLD reactor and coated with 1, 3, 5 and 10 cycles of mono-amine MLD, and 10 and 15 cycles of tri-amine MLD to vary film thickness and amine group deposition. An in-line mass spectrometer (Stanford Research Systems) attached to the reactor system monitored exiting gases.

[0072] Sorbents were characterized by nitrogen content (weight percent), thermal cyclic stability, monolayer uptake measurements, and absolute adsorption capacity. Nitrogen weight percent for each sample was obtained by LECO elemental analysis using approximately five to eight mg of each sample. Thermal cyclic stability tests were conducted using thermogravimetric analysis (TGA) to cycle between 80° C. and 30° C. At 80° C., the sample was held under pure argon for one hour. At 30° C., the sample was held under diluted CO.sub.2 (60% by volume) in argon for 30 minutes.

[0073] This cycle was repeated 25 times. Monolayer uptake measurements of the mono-amine were obtained using a Quantachrome Gas Sorption Analyzer and 30 to 40 mg of sample in a pure CO.sub.2 atmosphere for 30 minutes at 30° C.

[0074] Monolayer uptake data refers to μmol CO.sub.2/g sorbent physisorbed to the surface of the sample. Monolayer uptake is a similar measurement to adsorption capacity but is less indicative of the sorbent's actual capacity because of the test's stagnant gas environment that is unlikely to be seen in industrial applications. Therefore, absolute adsorption capacity measurements were taken using TGA under flowing inert and reactive gases. The sequential steps for each measurement included sorbent activation at 105° C. under pure argon for one hour followed by exposure to 40% (by volume) CO.sub.2 in argon at 30° C. for one hour and 26 minutes (equivalent to pure CO.sub.2 for one hour).

[0075] In the mass spectrometry (MS) trace for the mono-amine MLD shown in FIG. 6, there is proof of gas phase reactions for both of the reagent doses. Reactions occurred between (1) the aminopropyl-silane precursor molecule and the hydroxyl groups on the silica surface to produce ethanol or methanol as a byproduct, and (2) between water and the alkoxy groups of the deposited amine molecule to also produce ethanol or methanol as the leaving group. In the MS traces, the APTS-31 curve is the primary peak associated with the mono-amine. During the water dose in, the APTS-31 peak has an initial surge, followed by a change in slope ˜1 minute later. The change in slope followed by a plateauing trend indicates surface saturation of the water/ethoxy reactions. Additionally, due to the coupled nature of MLD reactions, the apparent reaction between water and some functional group indicates that some deposition of the mono-amine occurred on the surface prior to the water dose.

[0076] Alternatively, saturation of the surface was also deduced in the trace by the considerably large, and rapidly increasing APTS-31 trace at the beginning of the dose. Similarly, FIG. 7 is an example of a successful tri-amine/water MLD cycle to deposit an alkylamine network. The triamine-31 signal is most directly correlated with the tri-amine precursor. The initial surge in the triamine-31 signal followed by plateauing behavior during the tri-amine dose indicated surface saturation.

[0077] Nitrogen weight percent vs. cycle number data of the mono-amine and tri-amine sorbent materials presented further confirmation of the success and controllability of each of the MLD chemistries, as presented in at least FIG. 8 and FIG. 9. The nitrogen weight percent of the coated SiO.sub.2 samples increases from approximately 0.1% in the uncoated (zero cycles) sample to 1.42% over the addition of 10 cycles. 10 cycles of the tri-amine also has a weight percent of 1.40%. Therefore, both MLD chemistries were successful in depositing the alkylamine ligands.

[0078] The relationship of nitrogen content vs. mono-amine cycles also demonstrates an exponential trend from one to ten cycles, indicating potential surface saturation of MLD precursors at larger cycle numbers. Therefore, nitrogen content, proportional to the number of amine groups, of a CO.sub.2 sorbent can be directly controlled by the number of MLD cycles.

[0079] Thermal cycling between the desorption and adsorption temperature ranges was conducted for 25 cycles of both the 10-cycle mono-amine and 10-cycle tri-amine samples. Both 10-cycle samples adsorbed and desorbed CO.sub.2 in the aforementioned temperature ranges (FIG. 10). Adsorption is confirmed by the sharp increase in weight percent of the sample upon exposure to CO.sub.2 and desorption was confirmed by the decrease of that peak.

[0080] Both sorbents demonstrated the ability to regenerate amine active sites based on the constant amplitude in the mass percent change peaks over 25 cycles. If the amplitudes of subsequent peaks were to fall off/decrease, there would be evidence for amine group loss during the desorption steps. Therefore, MLD-synthesized, CO.sub.2 capture sorbents according to the present disclosure are able to regenerate within the desorption temperature range without noticeable depletion in amine groups.

[0081] MLD deposits an amine network that increases monolayer uptake of CO.sub.2 with increasing cycle numbers, which is also similar to the nitrogen content trend. The uncoated fumed silica exhibits a monolayer uptake of approximately 6.22 μmol CO.sub.2/g sorbent, 5 cycles of the mono-amine adsorbs 115 μmol CO.sub.2/g sorbent, and 10 cycles adsorbs 174 μmol CO.sub.2/g sorbent (FIG. 11). The increasing number of alkylamine ligands deposited by subsequent MLD cycles provides increased active sites for CO.sub.2 adsorption.

[0082] Absolute adsorption capacity also increases with cycle number. The 15-cycle triamine sorbent exhibits a significantly larger mass increase upon the introduction to a CO.sub.2 gas stream in comparison to the 10-cycle sorbent as seen in the TGA traces (FIG. 12). The adsorption capacity of a sorbent can be calculated from the mass change at 280 minutes in the TGA experiments by converting change in mass percent into mass using the initial mass of the sorbent, converting mass into mol of CO.sub.2, and dividing by the initial mass of the sorbent. The adsorption capacities were 0.382 mmol CO.sub.2/g sorbent and 1.86 mmol CO.sub.2/g sorbent, for 10 and 15 cycles of the tri-amine MLD, respectively, as presented in FIG. 13. MLD was successful in coating the silica substrate and increasing the adsorption capacity of the synthesized sorbents by increasing the cycle number.

[0083] The present disclosure can be embodied in other specific forms without departing from its spirit or essential characteristics. Thus, the described implementations are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.

[0084] It is to be understood that not necessarily all objects or advantages may be achieved under any embodiment of the disclosure. Those skilled in the art will recognize that the disclosed amine-functionalized solid sorbent and related methods may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught without achieving other objects or advantages as taught or suggested.

[0085] The skilled artisan will recognize the interchangeability of various disclosed features. Besides the variations described, other known equivalents for each feature can be mixed and matched by one of ordinary skill in this art to make or use an amine-functionalized solid sorbent under principles of the present disclosure. It will be understood by the skilled artisan that the features described may be adapted to other sorbent functionalization and related processes.