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WO2025194175A1 - Photocatalyseurs à base d'amine et procédés d'utilisation dans des systèmes de capture et de conversion de co2 réactif - Google Patents

Photocatalyseurs à base d'amine et procédés d'utilisation dans des systèmes de capture et de conversion de co2 réactif

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Publication number
WO2025194175A1
WO2025194175A1 PCT/US2025/020293 US2025020293W WO2025194175A1 WO 2025194175 A1 WO2025194175 A1 WO 2025194175A1 US 2025020293 W US2025020293 W US 2025020293W WO 2025194175 A1 WO2025194175 A1 WO 2025194175A1
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WO
WIPO (PCT)
Prior art keywords
amine
composition
product
aggregate composition
stream
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/020293
Other languages
English (en)
Inventor
Wade Adam BRAUNECKER
Noemi LEICK-MARIUS
Gerard Zachary CARROLL
Matthew Maurice Yung
Randy Douglas Cortright
James McWesley CRAWFORD
Sawyer HALINGSTAD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alliance for Sustainable Energy LLC
Original Assignee
Alliance for Sustainable Energy LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alliance for Sustainable Energy LLC filed Critical Alliance for Sustainable Energy LLC
Publication of WO2025194175A1 publication Critical patent/WO2025194175A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • This present disclosure relates to direct air capture (DAC) and photocatalytic CO2 conversion to useful intermediates and products.
  • An aspect of the present disclosure is an aggregate composition that includes a metal oxide particle, a nanoparticle constructed of a first metal, a second particle constructed of a second metal, and an amine, where the nanoparticle is positioned on a surface of at least one of the metal oxide particle, the second particle, or a combination thereof, the first metal includes a platinum -group metal, the second metal includes an earth- abundant material, the second metal is capable of absorbing light having a wavelength between 190 nm and 1000 nm, and the aggregate composition is capable of capturing CO2 and reacting the captured CO2 with H2 to form a product.
  • the nanoparticle may be positioned on the metal oxide particle.
  • the metal oxide particle may include at least one of TiCh , CeCh, ZnO, SnCh, or a combination thereof.
  • the metal oxide particle may have a diameter between 10 nm and 100 pm.
  • the platinum-group metal may be selected from the group consisting of ruthenium, platinum, and palladium, or a combination thereof.
  • the earth-abundant may be selected from the group consisting of copper, aluminum, and titanium, nickel, magnesium, or a combination thereof.
  • the amine may include at least one of a primary amine, a secondary amine, a tertiary amine, or a combination thereof.
  • the amine may include an alkyl amine.
  • the alkyl group of an alkyl amine may have between 1 and 10 carbon atoms.
  • an alkyl group ma include at least one of a methyl group, an ethyl group, a propyl group, a butyl group, or a combination thereof.
  • the amine may include an aminopolymer.
  • the aminopolymer may include at least one of a branched polyethyleneimine, a linear polyethyleneimine, or a combination thereof.
  • An aspect of the present disclosure is a system that includes a vessel having an inlet configured to receive a CO2 rich stream, a first outlet configured to release a CO2 lean stream, and a second outlet configured to release a product stream and a light source configured to emit light, where the vessel contains a composition capable of capturing CO2 and reacting the captured CO2 with H2 to form a product. Further, the vessel is capable of being repeatedly switched between a first setting and a second setting, where the first setting, configured to capture CO2, includes the inlet configured to receive the CO2 rich stream, the first outlet configured to release the CO2 lean stream, the second outlet configured to prevent the release of the product stream, and shielding the aggregate composition from the light.
  • the second setting configured react captured CO2 with H2 to form the product, includes the inlet configured to prevent receiving the CO2 rich stream, the first outlet configured to prevent releasing a CO2 lean stream, the second outlet configured to release the product stream, and irradiating the aggregate composition with the light.
  • An aspect of the present disclosure is a method utilizing a composition capable of converting CO2 to a product, where the method includes contacting the composition with a stream containing CO2, resulting in the adsorption of at least a portion of the CO2 onto a surface of the composition. Further, the method includes reacting the adsorbed CO2 with H2 to form the product, and removing the product from the composition, resulting in a gas stream containing the product. The reacting occurs due to irradiating the composition with a light.
  • a method may further include, after the contacting and before the reacting, purging the vessel of at least one of oxygen, air, non-adsorbed CO2, or a combination thereof.
  • Figure 1 illustrates amines suitable for aggregate compositions, according to some embodiments of the present disclosure.
  • FIGS 2A and 2B illustrate compositions, aggregates, according to some embodiments of the present disclosure.
  • Figure 3 illustrates a system, according to some embodiments of the present disclosure.
  • Figure 4 illustrates a method, according to some embodiments of the present disclosure.
  • Figure 5 illustrates proof-of-concept cycling data for efficient photo-desorption of CO2 in a direct air capture system, according to some embodiments of the present disclosure.
  • FIG. 6 illustrates photo-reactive direct air capture (DAC) results, according to some embodiments of the present disclosure.
  • Figure 7 illustrates powder XRD patterns of TiCh, Ru/TiCh, Ru/TiN/TiCh, Ru/TiN/TiO2/L-PEI, Ru/TiN/TiO2/B-PEI, according to some embodiments of the present disclosure.
  • Figure 8A illustrates N2 physisorption isotherms at 77 K for the 5wt% Ru/TiCh and 5wt% Ru/TiN/TiCh/L-PEI samples for p/po ⁇ 0.4, according to some embodiments of the present disclosure.
  • Figure 8B illustrates the pore size distributions extracted from the isotherms illustrated in Figure 8A and applying a DFT-based model, according to some embodiments of the present disclosure.
  • Figure 9 illustrates steady-state hydrocarbon production as a function of light intensity, according to some embodiments of the present disclosure.
  • CO2 concentration and hydrocarbon production are shown as a function of green light intensity, varied from 0.3 to 2.6 W/cm 2 in 10% increments.
  • Solid and dashed lines represent data for 5 wt.% Ru NPs on TiCh, with and without TiN, respectively. 10 seem of 2000 ppm CO2, 4% H2, balance N2.
  • Figure 10 illustrates (Top) Irradiation of the TiN/Ru/TiCh composite in an inert N2 atmosphere using a Prizmatix lime-green LED equipped with a collimating lens, according to some embodiments of the present disclosure.
  • Bottom Sample temperature recorded at 10% light intensity (left) and 100% light intensity (right).
  • Figure 11 illustrates the temperature of the TiN/Ru/TiCh composite and corresponding irradiance recorded at 530 nm as a function of relative LED intensity, according to some embodiments of the present disclosure.
  • the LED was focused to a 6 mm spot size.
  • Figures 12A-12C illustrate a CO2 desorption comparison for a single sorbent under dry and humid conditions, according to some embodiments of the present disclosure.
  • Experimental conditions 50 seem of 400 ppm CO2, 1.3 W/cm 2 green light irradiation, 10- minute adsorption (dark), followed by 2-minute desorption (light on).
  • Figures 12D and 12E illustrate a CO2 desorption comparison for a single set of humidity conditions across different sorbents, according to some embodiments of the present disclosure.
  • Experimental conditions 50 seem of 400 ppm CO2, 1.3 W/cm 2 green light irradiation, 10-minute adsorption (dark), followed by 2-minute desorption (light on).
  • Sample mass for each measurement Ru/TiN/TiCh (10 mg), Ru/TiN/TiO2/C3-NH2 (10 mg), Ru/TiN/TiCh/B-PEI (11 mg).
  • Figure 13 illustrates hydrocarbon production under steady-state flow with periodic light pulses, according to some embodiments of the present disclosure.
  • Figure 14A illustrates the photostability of different amine sorbents where after five cycles, the C3-NH2 system exhibits a nearly 50% reduction in CO2 capacity, according to some embodiments of the present disclosure.
  • Experimental conditions 50 seem of 400 ppm CO2, 1.3 W/cm 2 green light irradiation, 10-minute adsorption (dark), followed by 2- minute desorption (light on).
  • Figure 14B illustrates the photostability of different amine sorbents where over three cycles, no measurable degradation in CO2 capacity is observed for the B-PEI system.
  • Experimental conditions 50 seem of 400 ppm CO2, 1.3 W/cm 2 green light irradiation, 10- minute adsorption (dark), followed by 2-minute desorption (light on).
  • Figures 15A-15D illustrates relative hydrocarbon production vs. CO2 desorption in photo- RCC and photo-desorption cycles, according to some embodiments of the present disclosure.
  • Figures 15A and 15C illustrate raw LICOR and Enerac data, measuring the concentration of CO2 and CEE respectively, for five photo-RCC cycles using a B-PEI ( Figures 15A and 15B) and L-PEI composite ( Figures 15C and 15D) in forming gas, interspersed between two photo-desorption cycles in an inert N2 environment.
  • Figures 15B and 15D illustrate the relative amounts of CO2 and CEE desorbed from B-PEI ( Figures 15A and 15B) and L-PEI composites ( Figures 15C and 15D).
  • Figures 16A and 16B illustrate results from photo-desorption control experiments, according to some embodiments of the present disclosure. Following CO2 loading onto the Ru/Ti N/Ti O2/PEI composite in a 2000 ppm CO2 stream (10 seem total), the headspace was purged with 10 seem of pure N2 for 30 minutes. Subsequently, a green LED was used to illuminate the sample for 3 minutes to induce photo-desorption.
  • Figure 16A illustrates a blank control experiment was conducted without a sorbent to confirm background effects and compared to that of the L-PEI composite.
  • Figure 16B illustrates CO2 desorption profiles from composites containing L-PEI and B-PEI, demonstrating the impact of polymer structure on the kinetics of photo-desorption.
  • Figures 17A-17F illustrate TOF-MS analysis of effluent gas products, CO2, CEE, and CO, tracking mass-to-charge ratios (m/z) 44, 16, and 28, respectively for 10 mg of Ru/TiN/TiO2/L-PEI, according to some embodiments of the present disclosure.
  • Figures 17A-17C illustrate the results from a photo-desorption experiment: After CO2 loading in a 2000 ppm CO2 stream, the chamber was purged with N2 for 10 min, followed by 5 min of illumination, which induced CO2 desorption but yielded no detectable CEE or CO.
  • Figures 17D-17F illustrates the results from a photo-methanation experiment. After CO2 loading in a 2000 ppm CO2 stream, the chamber was purged with 5% Eb in N2 for 10 min, followed by 5 min of illumination, which induced some CO2 desorption but predominantly yielded CH 4 .
  • Figures 18A and 18B summarize properties and parameters for experiments reported herein. Columns 1-9 correspond to the following tests: 1 - “Amine-free methanation rxn (w/o TiN); 2 - “Amine-free methanation rxn (w/ TiN)”; 3 - “Small amine methanation rxn (continuous CO2)”; 4 - “Small amine methanation rxn (RCC purge)”; 5 - “Small amine photodesorption (humid)”; 6 - “B-polymer photodesorption (humid)”; 7 - “B-polymer methanation rxn (RCC purge, humid); 8 - “B-polymer methanation rxn (RCC purge, dry)”; 9 - “L-polymer methanation rxn (RCC purge, humid)”.
  • the photocatalyst is an aggregate of each of the following: (1) a support, e.g., mesoporous TiCh, which functions both as a high-surface- area support to facilitate efficient CO2 capture and conversion, and could double as a semiconducting photocatalyst; (2) a catalyst, e.g., a platinum-group catalytic metal, such as ruthenium, doped into the photocatalyst and present in nanoparticle form, acting as a ‘cocatalyst’ that enables efficient CO2 reduction; (3) an effective plasmonic light absorber utilizing earth-abundant materials like copper, aluminum, and/or titanium nanoparticles, enhancing the efficiency of visible photon harvesting into the semiconductor photocatalyst support; and (4) at least one of primary amine, secondary amine, or tert
  • an amine contained in an aggregate composition may be a small molecule amine that is covalently bonded to a support.
  • a bonded amine may be derived from an amino silane that has reacted with hydroxyl groups on a surface of a support. Examples of amines covalently bonded to a surface of a support are illustrated in Figure 1.
  • an amine may be a significantly larger molecule, such as an aminopolymer. Regardless, the choice of amine is characterized by favorable capture and release kinetics, resulting in effective capture of CO2 near catalytic sites for sufficient periods of time, to facilitate efficient photoreduction of the CO2 to useful products.
  • compositions that can capture CO2, react the CO2 to useful products, and release the products in gaseous form at high concentrations from the composition (e.g., between 75 mol% and 100 mol% or between 75 mol% and 99.9 mol%), as well as systems and methods for accomplishing those steps.
  • Figure 2A illustrates an exemplary composition, an aggregate 200A of at least three distinct particles, a first particle 210, a second particle 220, and a nanoparticle 215.
  • the aggregate 210 also includes an amine 240A.
  • the first particle 210 may be a metal oxide particle
  • the nanoparticle 215 may be constructed of a first metal
  • the second particle 220 may be constructed of a second metal.
  • the metal oxide particle 210 may serve the purpose of a support material for the nanoparticle 215, with the nanoparticle 215 positioned on various surfaces of the metal oxide particle 210 (as shown) and/or positioned on the second particle 220.
  • a metal oxide particle 210 may be constructed of at least one of TiCh , CeCh, ZnO, SnCh, or a combination thereof.
  • the first metal of a nanoparticle 215 may be a platinum-group metal, that among other things, catalyzes the reaction of CO2 with H2 to form various products, including at least one of methane, ethane, ethene, propane, propene, carbon monoxide, methanol, or a combination thereof.
  • the first metal of a nanoparticle 215 may include at least one of ruthenium, platinum, and palladium, or a combination thereof.
  • the second metal of a second particle 220 may include an earth-abundant material, acting as a plasmonic light absorber to the aggregate. In some embodiments of the present disclosure, the second metal of a second particle 220 may include at least one of copper, aluminum, and titanium, nickel, magnesium, or a combination thereof.
  • the amine 240A is illustrated to indicate that it is not covalently bonded to the first particle 210, the second particle 220, or the nanoparticle 215.
  • the amine 240A is bound to the aggregate 200A by an electrostatic interaction between the amine and at least one of the first particle 210, the second particle 220, the nanoparticle 215, or a combination thereof.
  • electrostatic interactions may include at least one of a dipole-dipole interaction, and iondipole interaction, a London dispersion force, hydrogen bonding, a Van der Waals force, or a combination thereof.
  • the amine 240A assists with the adsorption of the CO2 onto/into the aggregate 200A, enabling the catalyzed reaction of the CO2 with H2 to produce the product, e.g., CH4.
  • the metal oxide particle 210 acting as a support, the catalytic nanoparticle 215, the second particle 220 acting as a plasmonic light absorber, and the CCh-capturing amine 240A that enables the aggregate 210 to capture CO2, react the captured CO2 with H2 to form a product, when irradiated with light, and release the product in a concentrated gaseous form that can be easily used, upgraded, etc., in downstream processes.
  • physical contact and/or thermal contact between the first particle 210 and the second particle 220 provides heat transfer from the plasmonic light absorber to the metal oxide particle 210, the catalytic nanoparticle 215, and/or the captured CO2, further enabling the product-producing reaction to occur.
  • the amine 240A is electrostatically bound to at least one to the first particle 210, the second particle 220, or the nanoparticle 215.
  • Figure 2A illustrates another embodiment, where the amine 240B is covalently bound to the first particle (i.e., metal oxide particle) 210.
  • the amine (240A or 240B) may be at least one of a primary amine, a secondary amine, a tertiary amine, or a combination thereof.
  • an aminopolymer may include at least one of a branched polyethyleneimine, a linear polyethyleneimine, or a combination thereof.
  • an aminopolymer may have a molecular weight between 500 g/mol and 50,000 g/mol or between 600 g/mol and 2,500 g/mol.
  • the alkyl group of an alkyl amine may have between 1 and 10 carbon atoms.
  • the alkyl group of an alkyl amine may include at least one of a methyl group, an ethyl group, a propyl group, a butyl group, or a combination thereof.
  • an amine 240B is n-propylamine.
  • an aggregate 200 may include a combination of covalently bound alkyl amines and electrostatically bound aminopolymers.
  • the nanoparticle 215 is illustrated as being on a surface of a metal oxide particle (i.e., first particle) 210.
  • a nanoparticle 215 may be positioned on a surface of at least one of a first particle 210, a second particle 220, or a combination thereof.
  • each of the first particle 210, the second particle 220, and the nanoparticle 215 are illustrated as having spherical shapes. This is for illustrative purposes and is not intended to be limiting.
  • a first particle 210 may have a shape that includes at least one of at least one of a substantially spherical, a substantially cubic, a substantially polygonal, an irregular shape, or a combination thereof.
  • a second particle 220 may have a shape that includes at least one of at least one of a substantially spherical, a substantially cubic, a substantially polygonal, an irregular shape, or a combination thereof.
  • a nanoparticle 215 may have a shape that includes at least one of at least one of a substantially spherical, a substantially cubic, a substantially polygonal, an irregular shape, or a combination thereof.
  • a metal oxide particle 210 may have a diameter (and/or characteristic length, depending on the shape) between 10 nm and 100 pm or between 100 nm and 1 pm.
  • a second particle 220 may have a diameter (and/or characteristic length, depending on the shape)between 3 nm and 1000 nm or between 10 nm and 200 nm.
  • a nanoparticle 215 may have a diameter (and/or characteristic length, depending on the shape) between 3 nm and 1000 nm or between 10 nm and 200 nm.
  • a metal oxide particle 200 (i.e., a first particle), may be constructed of a mesoporous metal oxide.
  • a metal oxide particle may have a surface area between 25 m 2 /g and 3500 m 2 /g, or between 300 m 2 /g and 1200 m 2 /g, or between 20 m 2 /g and 50 m 2 /g.
  • an aggregate 200 may be characterized by a pore width between 5 A and 500 A or between 10 A and 200 A.
  • a second particle 220 may be present at a concentration between 0.1 wt% and 20 wt% or between 1 wt% and 10 wt%, relative to the total mass of the aggregate composition.
  • an amine (240A or 240B) is present at a concentration between 1 wt% and 65 wt% or between 1 wt% and 20 wt% relative to the total mass of the aggregate composition.
  • an aggregate composition 200 may include a first particle 210 of titanium dioxide, a nanoparticle 215 of ruthenium, a second particle of titanium nitride, and an aminopolymer that includes linear polyethyleneimine.
  • the nanoparticle 215 is positioned on a surface of the first particle 210
  • the titanium nitride is capable of absorbing light having a wavelength between 500 nm and 600 nm
  • the aggregate composition is capable of capturing CO2 and reacting the captured CO2 with H2 to form a product.
  • Figure 3 illustrates another aspect of the present disclosure, a system 300 configured to use an aggregate composition 210 as described above, designed for capturing CO2 and reacting the captured CO2 with H2 to form a product.
  • Potential sources of CO2 include directly from air (-400 ppm CO2), transportation tunnels (-1000 ppm CO2), flue gas from fossil fuel fired power plants (between 3 mol% and 15 mol% CO2), and fermentation processes (up to 85 mol% CO2).
  • Figure 3 illustrates a system 300 having two vessels (310A and 310B), each containing an aggregate composition (not shown). However, this is for illustrative purposes.
  • a system 300 may have only one vessel 310, two vessels (310A and 310B), or three or more vessels (310A to 310n), depending on the specific need, scale, etc.
  • a vessel 310 may be a three-dimensional shape having one or more walls that define and enclose an empty volume of which at least a portion may be filled with an aggregate composition 210. Examples of vessels 310 include, capped cylinders, piping, and/or tubing, as well as other shapes can include square and/or rectangular shapes.
  • a vessel 310 may be a packed-bed reactor, an annular reactor, a fluidized bed, a moving bed, a stirred-tank reactor, and/or a combination thereof.
  • a two-vessel (310A and 310B) system 300 may provide benefits over a single vessel system, in that while one vessel is configured to adsorb CO2, the other vessel may be configured to react the CO2 and/or remove the product from the second vessel.
  • Such a two-vessel configuration may, among other things, significantly increase the amount of time spent on-line producing product, thereby decreasing the unit cost and/or capital of the overall system.
  • each vessel may be connected to piping that enables the delivery of a CO2 rich stream 305 from a source to the vessels and piping configured for the rejection of a CO2 lean stream 315.
  • each vessel may be connected to piping that enables the delivery of an H2 rich stream 307 and piping configured for the rejection of an H2 lean stream 317.
  • each vessel may be connected to piping configured for the collection and distribution of a product stream 320.
  • each vessel (310A and 310B) may have a first inlet connected to the piping delivering the CO2 rich stream 305 or for delivering the H2 rich stream 307, a first outlet connected to piping for ejecting the CO2 lean stream (315A and 315B), or for ejecting the H2 lean stream (315A and 315B), and a second outlet connected to piping for collecting and distributing the product stream (320A and 320B).
  • FIG. 3 only one supply piping system and valve (VI) are illustrated for both the CO2 rich stream 305 and the H2 rich stream 307. This is because, if configured properly upstream, the same piping system, valve (VI), and the same inlets on a vessel may be used to direct both the CO2 rich stream 305 and the H2 rich stream 307 to the vessels (310A and 310B). Similarly, a single, piping system, outlet, and valve (V2 or V3) may be used to eject both the CO2 lean streams (315A or 315B) and the H2 lean stream (317A or 317B) from the vessels (310A and 310B).
  • Each vessel (310A and 310B) may have a dedicated line, outlet, and valve (V4 or V5) for ejecting the product stream (320 A or 320B) from its respective vessel (310 and 310B).
  • a two-vessel system 300 like that shown in Figure 3 may have a first feed system (piping, inlets, and valves) for delivering a CO2 rich stream 305 and a second feed system (piping, inlets, and valves) for delivering an H2 rich stream 307.
  • each vessel (310A and 310B) may be equipped with valves configured to switch each vessel (310A and 310B) repeatedly between three settings, a first setting for adsorbing (i.e., capturing) CO2, and a second setting for reacting CO2 to form the product, and a third setting for removing product from a vessel.
  • a single 3-way valve (VI) may be used to change which vessel receives the CO2 rich stream.
  • valve VI at the inlet of vessel 310A will be set to enable the flow of the CO2 rich stream into vessel 310A (while preventing the flow the CO2 rich stream in vessel 310B), valve V2 at the first outlet of the first vessel 310A will be opened to allow the release of a CO2 lean stream 315A resulting from the adsorption of the CO2 onto the aggregate composite, and valve V4 will be closed to force the CO2 rich stream to flow through the entire volume of the vessel 310A.
  • Vessel 310A, or at least the aggregate composite contained therein, will also be shielding from light.
  • valve VI at the inlet of vessel 310B will be set to prevent the flow of the CO2 rich stream in vessel 310B.
  • a 3 -way will be positioned to allow the H2 rich stream 307 to enter the second vessel 310B, while blocking the flow of H2 into the first vessel 310A.
  • Valve V3 at the first outlet of the second vessel 310B will also be open to allow the release of the H2 lean stream 317A resulting from the reaction of H2 with the CO2 adsorbed onto the aggregate composite, and valve V5 will be closed to force the H2 rich stream to flow through the entire volume of the vessel 310A.
  • Vessel 31 OB, or at least the aggregate composite contained therein, will be irradiated with light to induce the reaction.
  • product removal the position of the valves for the first vessel 310A operating in setting one, will remain the same.
  • a system 300 may include a vacuum system, configured to subject the contents of the vessels to pressures less than 1 atm-absolute.
  • vacuum is applied to the vessels (310A and/or 31 OB) in order to remove CO2, oxygen, and/or air after CO2 has been adsorbed onto the aggregate compositions and before contacting with H2 (at elevated temperature and with exposure to light).
  • vessels 310A and 310B may be continuously and reversibly cycled between one vessel adsorbing CO2, while the second vessel is reacting the CO2 with H2 and removing the resultant product.
  • a system may be cycled between once and 1000 times, or between once and 100 times.
  • a single light source 330 may be used to irradiate both vessels.
  • each vessel (310A and 310B) may be equipped with its own dedicated light source (330A and 330B).
  • Figure 3 illustrates a two-vessel system 300.
  • a system may have only a single vessel 310, wherein the single vessel 310 is cycled through the three settings: setting one - adsorb CO2, setting two - react CO2 to make product; and setting 3 - removing the product from the vessel.
  • a single-vessel system may have advantages over the more complicated two - or two-plus-systems, such as simplicity, portability, and/or flexible design for specific applications.
  • a system 300 may have vessel 300 having an inlet configured to receive a CO2 rich stream 305 or an H2 rich stream 307, first outlet configured to release a CO2 lean stream 315 or an H2 lean stream 317, and a second outlet configured to release a product stream.
  • a system will include a light source 330 configured to emit light 335.
  • the vessel 310 contains a composition, as previously described, capable of capturing CO2 and reacting the captured CO2 with H2 to form a product. Further, the vessel is capable of being repeatedly switched between the three settings.
  • the inlet When configured for the first setting, to capture CO2, the inlet is configured to receive the CO2 rich stream (and not receive H2), the first outlet is configured to release the CO2 lean stream, the second outlet is closed to force the CO2 to flow through the length of the vessel, and the aggregate composition is not irradiated with light.
  • the inlet When configured for the second setting, react the captured CO2 with H2 to form the product, the inlet is configured to receive the H2 rich stream (and not receive CO2), the first outlet is open to release the H2 lean stream, and the second outlet is closed to force the H2 to flow through the length of the vessel, and the aggregate composition is irradiated with light.
  • the inlet for either H2 rich or CO2 rich feed is closed, the first outlet for ejecting either lean CO2 or lean H2 is closed (to allow vacuum to be pulled in the vessel), and the second outlet to the vacuum system is opened.
  • Figure 4 illustrates a method for capturing CO2 using an aggregate composition as described above, reacting the captured CO2 with H2 to produce a product (e.g., CH4), followed by the release of the product as a concentrated gas (e.g., > 75 mol% product and up to 100 mol% product), according to some embodiments of the present disclosure.
  • the steps of this method may be repeated, i.e., cycled, multiple times.
  • the aggregate is capable of reversibly adsorbing/desorbing CO2 and desorbing the reaction product, i.e., CH4, thereby enabling the aggregate to be used repeatedly, and reducing at least one of the unit cost and/or unit capital of the system 200 (as described above).
  • a method 400 may several steps, beginning with the directing 405 of a CO2 rich stream to a vessel 310 containing an aggregate 200, resulting in the contacting 410 of the aggregate 200 with the CO2 contained in the CO2 rich stream, subsequently resulting in the adsorption of at least a portion of the CO2 onto a surface of the aggregate 200.
  • the aggregate 200 is sufficiently loaded with adsorbed CO2
  • purging 420 the vessel 310 may be achieved by either pulling a vacuum on the reactor 310 and/or by flowing an inert gas through the reactor 310.
  • purging 420 may be achieved by at least one of reducing the pressure in the vessel to less than 1.0 atm-absolute.
  • a method 400 may proceed with reacting 430 the adsorbed CO2 with H2 to form a product, e.g., methane.
  • the reacting 427 is achieved by directing 427 a stream of H2 to the vessel 310.
  • the H2 may be present in a stream at a concentration between 0.1 vol% H2 and 100 vol% H2, or between 1 vol% H2 and 25 vol% H2, or between 1 vol% H2 and 10 vol% H2.
  • reacting 430 may include irradiating the aggregate 200 with light while heating the aggregate 200 and adsorbed CO2 to an elevated temperature, while simultaneously passing a hydrogen gas stream over the aggregate 200.
  • the light used to irradiate the aggregate 200 may have a wavelength between 190 nm and 1000 nm or between 500 nm and 570 nm.
  • the method 400 may proceed with removing 440 the product from the vessel 310, resulting in the forming of a concentrated product stream 445.
  • Examples of compounds that may be formed from the reaction of the adsorbed CO2 with H2 include at least one of methane, ethane, ethene, propane, propene, carbon monoxide, methanol, or a combination thereof.
  • the concentration of CO2 in the CO2 rich stream directed to the vessel 310 containing the aggregate 200 may vary significantly, e.g., from less than a few hundred ppm of CO2 to as high as 85 mol% CO2.
  • CO2 rich stream may have a concentration of CO2 between 100 ppm and 5000 ppm or between 1500 ppm and 2500 ppm.
  • a CO2 rich stream may further contain water. As shown herein, some degree of humidity in the CO2 rich stream may promote faster adsorption of CO2 by the aggregate and/or faster reaction of the adsorbed CO2 with H2.
  • a CO2 rich stream may have a relative humidity between greater than 0% and less than 60%, or between 1% and 50%, or between 5% and 10%. Further, in some embodiments of the present disclosure, a CO2 rich stream may be provided to a vessel 310 containing an aggregate 200 at a temperature between 0 °C and 45 °C or between 15 °C and 35 °C. In some embodiments of the present disclosure, a CO2 rich stream may be provided to a vessel 310 containing an aggregate 210 at a pressure between 0.1 atm-absolute and 2.0 atm- absolute or between 0.8 atm-absolute and 1.2 atm-absolute.
  • reacting 430 the adsorbed CO2 with H2 may be performed at a temperature between 100 °C and 250 °C or between 130 °C and 200 °C.
  • the light provided during the reacting 430 may be provided at an intensity between 0.1 W/cm 2 and 100 W/cm 2 , or between 1 W/cm 2 and 10 W/cm 2 , or between 1 W/cm 2 and 5 W/cm 2 .
  • light provided during reacting 430 may be cycled on and off.
  • the light may be cycled such that a period of time that the light is on is between 1 second and 1 hour, or between 1 minute and 30 minutes, or between 1 minute and 10 minutes. In some embodiments of the present disclosure, the light may be cycled such that a period of time that the light is off is between 1 second and 2 hours, or between 1 minute and 1 hour, or between 10 minutes and 1 hour. In some embodiments of the present disclosure, the light may be cycled between on and off between 1 and 100 times, or between 1 and 50 times, or between 2 and 20 times.
  • a stream of H2 that is directed to a vessel containing CO2 adsorbed on an aggregate may further include water.
  • the water present in a stream comprising H2 may present at a relative humidity between greater than 0 % and less than 99 %, or between 0.1 % and 99 %, or between 1 % and 50 %, with an inert making up the remainder of the stream.
  • the removing 440 of the product stream 445 from the vessel 310 may be achieved by reducing the pressure in the vessel to less than 1.0 atm-absolute, or between 0.01 atm-absolute and 0.99 atm-absolute, or between 0.5 atm-absolute and 0.99 atm-absolute. In some embodiments of the present disclosure, the removing may be performed at a temperature between 15 °C and 250 °C or between 15 °C and 100 °C.
  • compositions and systems described herein successfully overcome performance-limiting factors prevalent in many existing DAC technologies.
  • the DAC systems described herein operate in a fully decentralized manner. Relying solely on electricity as the energy source for these cycles, this DAC system can function wherever there is access to solar, wind, and/or other forms of electricity.
  • the potential for enhanced energy efficiency, achieved by delivering heat exclusively to the local environment of the light absorber, may eliminate the necessity for widespread heating and pressurization.
  • Branched polyethyleneimine (B-PEI) had a number average molecular weight (M n ) of 600 g/mol, while linear PEI (L-PEI) had an M n of 2500 g/mol.
  • TiN Titanium nitride nanoparticles
  • NPs were purchased from US Research Nanomaterials, Inc. Previously, we characterized these NPs, where transmission electron microscopy revealed a heterogeneous morphology with an average size distribution centered around ⁇ 20 nm. Additionally, diffuse reflectance UV-Vis absorption spectroscopy showed a broad absorption spectrum spanning 380-750 nm.
  • PEI composites Nominally ⁇ 10 wt.% composites of polyethyleneimine (PEI) were prepared as follows: 21 mg of either branched PEI (B-PEI) or linear PEI (L-PEI) was stirred with 10.5 mg of TiN in 5 mL of methanol for 1 hour. Separately, 180 mg of Ru/TiCE was dispersed in methanol and stirred for 1 hour. The two solutions were then combined and stirred for an additional 3 hours. The resulting mixture was subjected to solvent removal using a rotary evaporator.
  • B-PEI branched PEI
  • L-PEI linear PEI
  • X-Ray Diffraction X-Ray Diffraction
  • Example 1 An aggregate composition comprising: a metal oxide particle; a nanoparticle comprising a first metal; a second particle comprising a second metal; and an amine, wherein: the nanoparticle is positioned on a surface of at least one of the metal oxide particle, the second particle, or a combination thereof, the first metal comprises a platinumgroup metal, the second metal comprises an earth-abundant material, the second metal is capable of absorbing light having a wavelength between 190 nm and 1000 nm, or between 400 nm and 700 nm, or between 500 nm and 600 nm, and the aggregate composition is capable of capturing CO2 and reacting the captured CO2 with H2 to form a product.
  • Example 2 The aggregate composition of Example 1, wherein the nanoparticle is positioned on the metal oxide particle.
  • Example 3 The aggregate composition of either Example 1 or Example 2, wherein the nanoparticle is positioned on the second particle.
  • Example 4 The aggregate composition of any one of Examples 1-3, wherein the metal oxide particle and the second particle are in physical contact.
  • Example 5 The aggregate composition of any one of Examples 1-4, wherein the metal oxide particle comprises a mesoporous metal oxide.
  • Example 6 The aggregate composition of any one of Examples 1-5, wherein the metal oxide particle has a surface area between 25 m 2 /g and 3500 m 2 /g, or between 300 m 2 /g and 1200 m 2 /g, or between 20 m 2 /g and 50 m 2 /g.
  • Example 7 The aggregate composition of any one of Examples 1-6, wherein the metal oxide particle is TiCh.
  • Example 8 The aggregate composition of any one of Examples 1-7, wherein the metal oxide particle comprises at least one of TiCh , CeCh, ZnO, SnCh, or a combination thereof.
  • Example 9 The aggregate composition of any one of Examples 1-8, wherein the metal oxide particle has a diameter between 10 nm and 100 pm or between 100 nm and 1 pm.
  • Example 10 The aggregate composition of any one of Examples 1-9, wherein the platinum-group metal is selected from the group consisting of ruthenium, platinum, and palladium, or a combination thereof.
  • Example 12 The aggregate composition of any one of Examples 1-11, wherein the nanoparticle has a diameter between 3 nm and 1000 nm or between 10 nm and 200 nm.
  • Example 13 The aggregate composition of any one of Examples 1-12, wherein the earth- abundant is selected from the group consisting of copper, aluminum, and titanium, nickel, magnesium, or a combination thereof.
  • Example 14 The aggregate composition of any one of Examples 1-13, wherein the second particle (i.e., light absorbing) is present at a concentration between 0.1 wt% and 20 wt% or between 1 wt% and 10 wt%, relative to the total mass of the aggregate composition.
  • the second particle i.e., light absorbing
  • Example 15 The aggregate composition of any one of Examples 1-14, wherein the second particle (i.e., light absorbing) has a diameter between 3 nm and 1000 nm or between 10 nm and 200 nm.
  • the second particle i.e., light absorbing
  • Example 16 The aggregate composition of any one of Examples 1-15, wherein the amine comprises at least one of a primary amine, a secondary amine, a tertiary amine, or a combination thereof.
  • Example 17 The aggregate composition of any one of Examples 1-16, wherein the amine is covalently bonded to the metal oxide.
  • Example 18 The aggregate composition of any one of Examples 1-17, wherein the amine comprises an alkyl amine.
  • Example 19 The aggregate composition of any one of Examples 1-18, wherein an alkyl group of the alkyl amine has between 1 and 10 carbon atoms.
  • Example 20 The aggregate composition of any one of Examples 1-19, wherein an alkyl group comprises at least one of a methyl group, an ethyl group, a propyl group, a butyl group, or a combination thereof.
  • Example 21 The aggregate composition of any one of Examples 1 -20, wherein the amine is n-propylamine.
  • Example 22 The aggregate composition of any one of Examples 1-1217, wherein the amine is present at a concentration between 1 wt% and 65 wt% or between 1 wt% and 20 wt% relative to the total mass of the aggregate composition.
  • Example 23 The aggregate composition of any one of Examples 1 -22, wherein the amine is bound to the aggregate composition by an electrostatic interaction between the amine and at least one of the first particle, the second particle, or a combination thereof.
  • Example 24 The aggregate composition of any one of Examples 1-23, wherein the electrostatic interaction comprises at least one of a dipole-dipole interaction, and ion-dipole interaction, a London dispersion force, hydrogen bonding, a Van der Waals force, or a combination thereof.
  • Example 25 The aggregate composition of any one of Examples 1 -24, wherein the amine comprises an aminopolymer.
  • Example 26 The aggregate composition of any one of Examples 1-25, wherein the aminopolymer comprises at least one of a branched polyethyleneimine, a linear polyethyleneimine, or a combination thereof.
  • Example 27 The aggregate composition of any one of Examples 1-26, wherein the molecular weight of the aminopolymer is between 500 g/mol and 50,000 g/mol or between 600 g/mol and 2,500 g/mol.
  • Example 28 The aggregate composition of any one of Examples 1-27, wherein the aminopolymer is present at a concentration between 1 wt% and 65 wt% or between 1 wt% and 20 wt% relative to the total mass of the aggregate composition.
  • Example 29 The aggregate composition of any one of Examples 1-28, wherein the first particle has a shape that is at least one of substantially spherical, cubic, polygonal, an irregular shape, or a combination thereof.
  • Example 30 The aggregate composition of any one of Examples 1-29, wherein the second particle has a shape that is at least one of substantially spherical, cubic, polygonal, an irregular shape, or a combination thereof.
  • Example 31 The aggregate composition of any one of Examples 1-30, wherein the nanoparticle has a shape that is at least one of substantially spherical, cubic, polygonal, an irregular shape, or a combination thereof.
  • Example 32 The aggregate composition of any one of Examples 1-31, further comprising a pore width between 5 A and 500 A or between 10 A and 200 A.
  • Example 33 The aggregate composition of any one of Examples 1-32, wherein the product comprises at least one of methane, ethane, ethene, propane, propene, carbon monoxide, methanol, or a combination thereof.
  • Example 34 An aggregate composition comprising: a metal oxide particle; a nanoparticle comprising a platinum-group metal; a second particle comprising an earth- abundant material; and an amine, wherein: the nanoparticle is positioned on a surface of at least one of the metal oxide particle, the second particle, or a combination thereof, the second particle is capable of absorbing light having a wavelength between 190 nm and 1000 nm, or between 400 nm and 700 nm, or between 500 nm and 600 nm, and the aggregate composition is capable of capturing CO2 and reacting the captured CO2 with H2 to form a product.
  • Example 35 The aggregate composition of Example 34, wherein the metal oxide particle and the second particle are in physical contact.
  • Example 36 The aggregate composition of either Example 34 or 35, wherein the metal oxide particle comprises a mesoporous metal oxide.
  • Example 37 The aggregate composition of any one of Examples 34-36, wherein the metal oxide particle comprises at least one of TiCh , CeCh, ZnO, SnCh, or a combination thereof.
  • Example 38 The aggregate composition of any one of Examples 34-37, wherein the metal oxide particle has a diameter between 10 nm and 100 pm or between 100 nm and 1 pm.
  • Example 39 The aggregate composition of any one of Examples 34-38, wherein the amine is covalently bonded to the metal oxide particle.
  • Example 40 The aggregate composition of any one of Examples 34-39, wherein the amine is bound to the aggregate composition by an electrostatic interaction between the amine and at least one of the metal oxide particle, the second particle, or a combination thereof.
  • Example 41 The aggregate composition of any one of Examples 34-40, wherein the metal oxide particle has a shape that is at least one of substantially spherical, cubic, polygonal, or a combination thereof.
  • Example 42 An aggregate composition comprising: a first particle comprising titanium dioxide; a nanoparticle comprising ruthenium; a second particle comprising titanium nitride; and and an aminopolymer comprising linear polyethyleneimine, wherein: the nanoparticle is positioned on a surface of the first particle, the titanium nitride is capable of absorbing light having a wavelength between 500 nm and 600 nm, and the aggregate composition is capable of capturing CO2 and reacting the captured CO2 with H2 to form a product.
  • Example 44 The aggregate composition of either Example 42 or 43, wherein the second particle (i.e., light absorbing) is present at a concentration between 1 wt% and 10 wt%, relative to the total mass of the aggregate composition.
  • Example 45 The aggregate composition of any one of Examples 42-44, wherein the amine is present at a concentration between 1 wt% and 20 wt% relative to the total mass of the aggregate composition.
  • Example 46 A system comprising: a vessel having an inlet configured to receive a CO2 rich stream, a first outlet configured to release a CO2 lean stream, and a second outlet configured to release a product stream; and a light source configured to emit light, wherein: the vessel contains a composition capable of capturing CO2 and reacting the captured CO2 with H2 to form a product, the vessel is capable of being repeatedly switched between a first setting and a second setting, the first setting, configured to capture CO2, comprises: the inlet configured to receive the CO2 rich stream, the first outlet configured to release the CO2 lean stream, the second outlet configured to prevent the release of the product stream, and shielding the aggregate composition from the light; the second setting, configured react captured CO2 with H2 to form the product, comprises: the inlet configured to prevent receiving the CO2 rich stream, the first outlet configured to prevent releasing a CO2 lean stream, the second outlet configured to release the product stream, and irradiating the aggregate composition with the light.
  • Example 47 The system of Example 46, further comprising a vacuum system configured to remove at least one of the product streams, oxygen, air, CO2, or a combination thereof from the vessel.
  • Example 48 The system of either Example 46 or 47, further comprising a plurality of valves configured to switch the vessel between the first setting and the second setting.
  • Example 49 A system comprising: a first vessel having an inlet configured to receive a CO2 rich stream, an outlet configured to release a first CO2 lean stream, and an outlet configured to release a first product stream; a second vessel having an inlet configured to receive the CO2 rich stream, an outlet configured to release a second CCh-lean stream, and an outlet configured to release a second product stream; and a light source configured to emit light, wherein: both the first vessel and the second vessel contain a composition capable of capturing CO2 and reacting the captured CO2 with H2 to form a product, both the first vessel and the second vessel are capable of being repeatedly switched between a first setting and a second setting, when the first vessel is in the first setting, the second vessel is in the second setting, when the first vessel is in the second setting, the second vessel is in the first setting, the first setting, configured to capture CO2, comprises: an open inlet configured to receive a CO2 rich stream, an open outlet configured to release a CO2 lean stream, a closed outlet configured to prevent the release of
  • Example 50 The system of Example 49, further comprising a vacuum system configured to removing the product streams from the vessels.
  • Example 51 The system of either Example 48 or 49, further comprising a plurality of valves configured to switch the vessels between the settings.
  • Example 52 A method utilizing a composition capable of converting CO2 to a product, the method comprising: contacting the composition with a stream containing CO2, resulting in the adsorption of at least a portion of the CO2 onto a surface of the composition; reacting the adsorbed CO2 with H2 to form the product; and removing the product from the composition, resulting in a gas stream containing the product, wherein: the reacting occurs due to irradiating the composition with a light.
  • Example 53 The method of Example 52, wherein the light has a wavelength between 190 nm and 1000 nm.
  • Example 54 The method of either Example 52 or 53, wherein, the product comprises at least one of methane, ethane, ethene, propane, propene, carbon monoxide, methanol, or a combination thereof.
  • Example 55 The method of any one of Examples 52-54, wherein the contacting and reacting are performed in a vessel.
  • Example 56 The method of any one of Examples 52-55, further comprising, after the contacting and before the reacting, purging the vessel of any oxygen, air, and/or nonadsorbed CO2.
  • Example 57 The method of any one of Examples 52-56, wherein the stream containing CO2 contains a concentration of CO2 between 100 ppm and 5000 ppm or between 1500 ppm and 2500 ppm.
  • Example 58 The method of any one of Examples 52-57, wherein the stream containing CO2 further contains water.
  • Example 59 The method of any one of Examples 52-58, wherein the stream containing CO2 is at a relative humidity between greater than 0% and less than 60%, or between 1% and 50%, or between 5% and 10%.
  • Example 60 The method of any one of Examples 52-59, wherein the stream containing CO2 is at a temperature between 0 °C and 45 °C or between 15 °C and 35 °C.
  • Example 61 The method of any one of Examples 52-60, wherein the stream containing CO2 is at a pressure between 0.1 atm-absolute and 2.0 atm-absolute or between 0.8 atm- absolute and 1.2 atm-absolute.
  • Example 62 The method of any one of Examples 52-61, wherein the purging is achieved by at least one of reducing the pressure in the vessel to less than 1.0 atm-absolute or by passing an inert gas through the vessel.
  • Example 63 The method of any one of Examples 52-62, wherein the reacting is performed at a temperature between 100 °C and 250 °C or between 130 °C and 200 °C.
  • Example 64 The method of any one of Examples 52-63, wherein the light has a wavelength between 190 nm and 1000 nm.
  • Example 65 The method of any one of Examples 52-64, wherein the light is provided at an intensity between 0.1 W/cm 2 and 100 W/cm 2 , or between 1 W/cm 2 and 10 W/cm 2 , or between 1 W/cm 2 and 5 W/cm 2 .
  • Example 66 The method of any one of Examples 52-65, wherein, during the reacting, the light is cycled on and off.
  • Example 67 The method of any one of Examples 52-66, wherein the light is on for period of time between 1 second and 1 hour, or between 1 minute and 30 minutes, or between 1 minute and 10 minutes.
  • Example 68 The method of any one of Examples 52-67, wherein the light is off for period of time between 1 second and 2 hours, or between 1 minute and 1 hour, or between 10 minutes and 1 hour.
  • Example 69 The method of any one of Examples 52-68, wherein the light is cycled between on and off between 1 and 100 times, or between 1 and 50 times, or between 2 and 20 times.
  • Example 70 The method of any one of Examples 52-69, wherein, during the reacting, passing a stream comprising Eb over the composition.
  • Example 71 The method of any one of Examples 52-70, wherein the Eb in the stream is present at a concentration between 0.1 vol% Eb and 50 vol% Eb, or between 1 vol% Eb and 25 vol% Eb, or between 1 vol% Eb and 10 vol% Eb.
  • Example 72 The method of any one of Examples 52-71, wherein the stream comprising Eb further comprises water.
  • Example 73 The method of any one of Examples 52-72, wherein the water present in the stream comprising Eb is present at a relative humidity between greater than 0 % and less than 99 %, or between 0.1 % and 99 %, or between 1 % and 50 %.
  • Example 74 The method of any one of Examples 52-73, wherein the remainder of the stream comprising Eb is an inert.
  • Example 75 The method of any one of Examples 52-74, wherein the removing is achieved by reducing the pressure in the vessel to less than 1.0 atm-absolute, or between 0.01 atm-absolute and 0.99 atm-absolute, or between 0.5 atm-absolute and 0.99 atm- absolute.
  • the term “substantially” is used to indicate that exact values are not necessarily attainable.
  • 100% conversion of a reactant is possible, yet unlikely.
  • Most of a reactant may be converted to a product and conversion of the reactant may asymptotically approach 100% conversion. So, although from a practical perspective 100% of the reactant is converted, from a technical perspective, a small and sometimes difficult to define amount remains.
  • that amount may be relatively easily defined by the detection limits of the instrument used to test for it. However, in many cases, this amount may not be easily defined, hence the use of the term “substantially”.
  • the term “substantially” is defined as approaching a specific numeric value or target to within 20%, 15%, 10%, 5%, or within 1% of the value or target. In further embodiments of the present invention, the term “substantially” is defined as approaching a specific numeric value or target to within 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, or 0.1% of the value or target.
  • the term “about” is used to indicate that exact values are not necessarily attainable. Therefore, the term “about” is used to indicate this uncertainty limit. In some embodiments of the present invention, the term “about” is used to indicate an uncertainty limit of less than or equal to ⁇ 20%, ⁇ 15%, ⁇ 10%, ⁇ 5%, or ⁇ 1% of a specific numeric value or target. In some embodiments of the present invention, the term “about” is used to indicate an uncertainty limit of less than or equal to ⁇ 1%, ⁇ 0.9%, ⁇ 0.8%, ⁇ 0.7%, ⁇ 0.6%, ⁇ 0.5%, ⁇ 0.4%, ⁇ 0.3%, ⁇ 0.2%, or ⁇ 0.1% of a specific numeric value or target.
  • the terms “A or B” and “A and/or B” are intended to encompass A, B, or ⁇ A and B ⁇ . Further, the terms “A, B, or C” and “A, B, and/or C” are intended to encompass single items, pairs of items, or all items, that is, all of A, B, C, ⁇ A and B ⁇ , ⁇ A and C ⁇ , ⁇ B and C ⁇ , and ⁇ A and B and C ⁇ .
  • the term “or” as used herein means “and/or.”
  • language such as “at least one of X, Y, and Z,” “at least one of X, Y, or Z,” “at least one or more of X, Y, and Z,” “at least one or more of X, Y, or Z,” “at least one or more of X, Y, and/or Z,” or “at least one of X, Y, and/or Z,” is intended to be inclusive of both a single item (e.g., just X, or just Y, or just Z) and multiple items (e.g., ⁇ X and Y ⁇ , ⁇ X and Z ⁇ , ⁇ Y and Z ⁇ , or ⁇ X, Y, and Z ⁇ ).
  • the phrase “at least one of’ and similar phrases are not intended to convey a requirement that each possible item must be present, although each possible item may be present.
  • inventive aspects lie in less than all features of a single foregoing disclosed embodiment, configuration, or aspect. While certain aspects of conventional technology have been discussed to facilitate disclosure of some embodiments of the present invention, the Applicants in no way disclaim these technical aspects, and it is contemplated that the claimed invention may encompass one or more of the conventional technical aspects discussed herein. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate aspect, embodiment, or configuration.

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Abstract

La présente divulgation concerne une composition d'agrégat qui comprend une particule d'oxyde métallique, une nanoparticule constituée d'un premier métal, une deuxième particule constituée d'un deuxième métal, et une amine, la nanoparticule étant positionnée sur une surface d'au moins l'une parmi la particule d'oxyde métallique, la deuxième particule, ou une combinaison de celles-ci, le premier métal comprenant un métal du groupe du platine, le deuxième métal comprenant un matériau abondant sur terre, le deuxième métal pouvant absorber la lumière ayant une longueur d'onde comprise entre 190 nm et 1000 nm, et la composition d'agrégat étant apte à capturer CO2 et faire réagir le CO2 capturé avec H2 pour former un produit.
PCT/US2025/020293 2024-03-15 2025-03-17 Photocatalyseurs à base d'amine et procédés d'utilisation dans des systèmes de capture et de conversion de co2 réactif Pending WO2025194175A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
US20080261805A1 (en) * 2005-09-22 2008-10-23 Toto Ltd. Photocatalytic Titanium Dioxide Microparticle, Dispersion Liquid Thereof and Process for Producing the Same
US20140179810A1 (en) * 2011-07-28 2014-06-26 Sogang University Research Foundation Method for reducing carbon dioxide by using sunlight and hydrogen and apparatus for same
US20160375432A1 (en) * 2013-07-03 2016-12-29 Gwangju Institute Of Science And Technology Photocatalyst complex
US20200085060A1 (en) * 2018-09-14 2020-03-19 Fuji Xerox Co., Ltd. Plant protection agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080261805A1 (en) * 2005-09-22 2008-10-23 Toto Ltd. Photocatalytic Titanium Dioxide Microparticle, Dispersion Liquid Thereof and Process for Producing the Same
US20140179810A1 (en) * 2011-07-28 2014-06-26 Sogang University Research Foundation Method for reducing carbon dioxide by using sunlight and hydrogen and apparatus for same
US20160375432A1 (en) * 2013-07-03 2016-12-29 Gwangju Institute Of Science And Technology Photocatalyst complex
US20200085060A1 (en) * 2018-09-14 2020-03-19 Fuji Xerox Co., Ltd. Plant protection agent

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