Patent Application
20190309425
In one aspect, a flow-through electrolysis cell is provided. The cell includes a cathode including a hierarchical nanoporous metal; an anode including a metallic mesh; and an ion-exchange membrane; wherein the hierarchical nanoporous metal is a catalytic metal for reduction of a reactant which contacts the hierarchical nanoporous metal.
In some embodiments, the hierarchical nanoporous metal may include one or more of copper, platinum, silver, gold, nickel, iron, and zinc. In some embodiments, the hierarchical nanoporous metal may be copper. In some embodiments, the hierarchical nanoporous metal may be a dealloyed metal alloy. In some embodiments where the hierarchical nanoporous metal is hierarchical nanoporous copper, the hierarchical nanoporous copper may be a dealloyed aluminum-copper alloy. In any of the above embodiments, the hierarchical nanoporous metal may have an average nanopore diameter of about 10 nm to about 500 nm and an average macropore diameter of about 500 nm to about 106 nm.
In some embodiments, the metallic mesh may include one or more of platinum, porous platinum, iridium, nickel, iron, palladium, carbon, and boron-doped carbon/diamond. In some embodiments, the metallic mesh may include platinum. In any of the above embodiments, the metallic mesh may include a plurality of pores having an average pore diameter of about 1 μm to about 10,000 μm.
In some embodiments, the flow-through electrolysis cell may further include a reference electrode. In some embodiments, the reference electrode may include one or more of silver, copper, platinum, palladium, mercury, and hydrogen. In some embodiments, the reference electrode may include silver.
In any of the above embodiments, the reactant may be CO2.
In any of the above embodiments, the cathode may contain a first face and an opposite facing second face, the flow-through electrolysis cell may include a first electrolytic fluid input proximal to the first face and a first electrolytic fluid output proximal to the second face, such that the cell is configured to convey an electrolyte through the hierarchical nanoporous metal.
In some embodiments, the electrolyte may include CO2. In some embodiments, the electrolyte may be a KHCO3 solution. In some embodiments, the electrolyte may be a KH2PO4/K2HPO4 buffer. In some embodiments, the KH2PO4, K2HPO4, or KHCO3 may be present from 0.1 M to 5 M.
In some embodiments, the ion-exchange membrane may be an anion exchange membrane (AEM). In other embodiments, the ion-exchange membrane may be a proton exchange membrane (PEM).
In another aspect, a method is provided of reducing CO2. The method includes contacting CO2 with a cathode housed in a flow-through electrolysis cell; wherein the cathode comprises a hierarchical nanoporous metal; wherein the flow-through electrolysis cell comprises an anode and an ion-exchange membrane, wherein the anode comprises a metallic mesh; wherein the CO2 is dissolved in an electrolyte; and wherein contacting CO2 with the cathode comprises flowing the electrolyte through the cathode.
In another embodiment, the method includes reducing CO2 to produce a hydrocarbon, an aldehyde, an alcohol, a ketone, a carboxylic acid, or a mixture of any two or more thereof. Where the product is a hydrocarbon, the hydrocarbon produced may include ethylene, methane, or a mixture thereof. In some of the above embodiments, the method may include monitoring the composition of product using an analytical technique. In another embodiment, the analytical technique is gas chromatography mass spectrometry (GCMS).
In any of the above embodiments, the flowing may include applying a pressure gradient across the cathode, in a further embodiment the pressure gradient may be from about 0.1 atm to about 10 atm. In any of the above embodiments, the electrolyte flows through the cathode at a velocity of less than about 1 cm/s.
In any of the above embodiments, the electrolyte may contain KH2PO4, K2HPO4, or KHCO3. In any of the above embodiments, the KH2PO4, K2HPO4, or KHCO3 may be present in the electrolyte from 0.1 to 5 M. In some embodiments, the electrolyte is saturated with CO2.
In some embodiments, the cathode may include one or more of copper, platinum, silver, gold, nickel, iron, and zinc. In some embodiments, the anode may include one or more of platinum, palladium, carbon and boron-doped/diamond.
Among those benefits and improvements that have been disclosed, other objects and advantages of this invention may become apparent from the following description taken in conjunction with the accompanying figures. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative and may be embodied in various forms. In addition, each of the examples given in connection with the various embodiments is intended to be illustrative, and not restrictive. Any alterations and further modifications of the features illustrated herein, and any additional applications of the principles illustrated herein, which can normally occur to one skilled in the relevant art and having possession of this disclosure, are to be considered within the scope of the application.
Throughout the specification and claims, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise. The phrases “in one aspect” and “in some aspects” and the like, as used herein, do not necessarily refer to the same embodiment(s), though they may. Furthermore, the phrases “in another aspect” and “in some other aspects” as used herein do not necessarily refer to a different aspect (embodiment), although they may. Thus, as described below, various aspects (embodiments) of the invention may be readily combined, without departing from the scope or spirit of the invention.
In addition, as used herein, the term “or” is an inclusive “or” operator, and is equivalent to the term “and/or,” unless the context clearly dictates otherwise. The term “based on” is not exclusive and allows for being based on additional factors not described, unless the context clearly dictates otherwise. In addition, throughout the specification, the meaning of “a,” “an,” and “the” include plural references. The meaning of “in” includes “in” and “on.”
As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.
As used herein, use of the term “flow-through” to describe an electrolysis cell describes a cell wherein electrolyte flows through an electrode rather than “flowing-by” the electrode.
As used herein, the term “hierarchical nanoporous” (“hnp”) is used to describe a metal that possess a three-dimensional structure of randomly interpenetrating macropores, nanopores and channels, as illustrated by the photograph in
As used herein, the term “direct ink writing” refers to a technique whereby a material may be extruded from a small nozzle while the nozzle is moved across a platform. The hnp material may be produced using this technique by depositing a material from the nozzle and drawing the hnp shape onto the platform, layer by layer.
As used herein, the term “dealloying” or “dealloying a metal alloy” refers to the selective corrosion of one or more components of the alloy and subsequent removal of the corroded component(s).
As used herein, the term “half-cell” refers to a portion of the flow-through electrolysis cell that is separated by an ion-exchange membrane from the rest of the flow-through electrolysis cell, or the other half-cell. The electrolyte cannot flow from one half-cell into the other half-cell, as the ion-exchange membrane is not permeable to water. One half-cell contains the cathode, while the other half-cell contains the anode.
Disclosed herein is a flow-through electrolysis cell. The flow-through electrolysis cell is configured to catalyze the electrochemical reduction of a reactant, such as CO2, which is dissolved in an electrolyte. Catalysis occurs when the electrolyte carries CO2 into contact with the cathode of the flow-through electrolysis cell. The cathode may be constructed with a hierarchical nanoporous metal, such as hierarchical nanoporous copper (hnp-Cu). The hierarchical nanoporous copper cathode is permeable to the electrolyte allowing the solution to flow-through the cathode, which allows for increased mass-transport, increased surface area for catalysis to occur, and improved Faradaic efficiency, and selectivity. The flow-through concept takes advantage of the volumetric porosity of the electrode. The continuous flow of electrolyte through the cathode facilitates improved contact of the CO2 with the catalyst when compared to traditional “flow-by” designs. Flow-by and flow-through setups are contrasted in
The electrochemical reduction of CO2 produces a variety of industrially useful compounds such as ethylene. Ethylene is a sought after feedstock in the chemical industry for the production of plastics, surfactants, detergents, polymers and other industrially important products. Nano-cube Cu surfaces provide much higher selectivity towards ethylene than smooth Cu surfaces do. Thus, the use of hierarchical nanoporous Cu to catalyze the reduction of CO2 in the disclosed flow-through cell allows for targeted production of ethylene while realizing high current densities. The flow-through electrolysis cell with an hnp-Cu catalyst allows for accessing a higher catalyst surface area than in a flow-by, or non-nanoporous system. Thus, low reaction rates at lower overpotential can be tolerated, while still achieving high conversion rates.
Referring to
The metallic mesh anode (18) may be positioned inside of a frame (11). Between the frame (11) and the AEM (9) is positioned a gasket (10). On the side of the frame (11) opposite gasket (10) is a gasket (12). The gasket (12) is positioned between the frame (11) and an endcap (13). Electrolyte-in line (14) passes through the endcap (13) through a fourth aperture (41) and an electrolyte-out line (15) passes through the endcap (13) through a fifth aperture (42).
A potentiostat (47) is connected to the cell to provide a potential to the electrodes. In some embodiments, the voltage provided by the potentiostat (47) is about 0.1V to about 10V. The power source (48) operates in constant current mode or constant voltage mode or the power source (48) is a pulsed power source.
Referring to
The metallic mesh anode (34) may be positioned within a frame (29). Between the frame (29) and the PEM (27) is positioned a gasket (28). On the side of the frame (29) opposite gasket (28) may be positioned a gasket (30). The gasket (30) is positioned between frame (29) and an endcap (31). An electrolyte-in line (32) passes through the endcap (31) through a fourth aperture (45) and an electrolyte-out line (33) passes through the endcap (31) through a fifth aperture (46).
The voltage provided by the potentiostat (50) is from about 0.1V to about 10V. The power source (49) operates in constant current mode or constant voltage mode or the power source (49) is a pulsed power source.
The frames, reservoirs, and/or endcaps may be individually constructed of any suitable material. Suitable materials include, but are not limited to polymers, glasses, ceramics, metals, and composite materials. In some embodiments, the frames, reservoirs, and/or endcaps may be constructed of a polymer such as, but not limited to, polyolefins, polyacrylates, and/or polycarbonates. The gaskets may be constructed of a sealing material such as natural or synthetic rubbers.
In one aspect, a flow-through electrolysis cell is provided. The cell includes a cathode including a hierarchical nanoporous metal; an anode including a metallic mesh; and an ion-exchange membrane; wherein the hierarchical nanoporous metal is a catalytic metal for reduction of a reactant which contacts the hierarchical nanoporous metal.
In some embodiments, the hierarchical nanoporous metal includes one or more of copper, platinum, silver, gold, nickel, iron, and zinc. In some embodiments, the hierarchical nanoporous metal may be copper. In some embodiments, the hierarchical nanoporous metal is a dealloyed metal alloy. Where the hierarchical nanoporous metal is hierarchical nanoporous copper, the hierarchical nanoporous copper may be a dealloyed aluminum-copper alloy. The hierarchical nanoporous metal may have an average nanopore diameter of about 10 nm to about 500 nm and an average macropore diameter of about 500 nm to about 106 nm. In some embodiments, the hierarchical nanoporous metal may have an average nanopore diameter of about 10 nm to about 200 nm and an average macropore diameter of about 500 nm to about 106 nm.
The metallic mesh may include one or more of platinum, porous platinum, iridium, nickel, iron, palladium, carbon, and boron-doped carbon/diamond. In some embodiments, the metallic mesh includes platinum. The metallic mesh may include a plurality of pores having an average pore diameter of about 1 μm to about 10,000 μm.
The flow-through electrolysis cell may also include a reference electrode. In some embodiments, the reference electrode may include one or more of silver, copper, platinum, palladium, mercury, and hydrogen. In some embodiments, the reference electrode includes silver.
In any of the above embodiments, the reactant is CO2.
The cathode may have a first face and an opposite facing second face, the flow-through electrolysis cell further including a first electrolytic fluid input proximal to the first face and a first electrolytic fluid output proximal to the second face, such that the cell is configured to convey an electrolyte through the hierarchical nanoporous metal.
As noted above, the electrolyte may include dissolved CO2 as a reactant. The electrolyte may include a salt such as KHCO3, or a buffer such as KH2PO4/K2HPO4. In some embodiments, the salt and/or buffer may be present from 0.1 M to 5 M, preferably between 0.1 M and 1 M.
The ion-exchange membrane may be an anion exchange membrane (AEM), or a proton exchange membrane (PEM) depending upon the configuration of the cell.
In another aspect, a method of reducing CO2 is provided using the flow-through electrolysis cell described herein. The method includes contacting the CO2 with a cathode housed in a flow-through electrolysis cell, where the cathode includes a hierarchical nanoporous metal. The flow-through electrolysis cell includes an anode and an ion-exchange membrane, where the anode includes a metallic mesh. In such methods, the CO2 is dissolved in an electrolyte, and the contacting CO2 with the cathode includes flowing the electrolyte through the cathode.
In some embodiments, the CO2 is dissolved in the electrolyte by bubbling CO2 gas into the electrolyte to saturate the electrolyte with CO2. In some embodiments, the CO2 is present in the electrolyte at a concentration of about 0.05 cm3/ml electrolyte to about 5.0 cm3/ml electrolyte. In some embodiments, the electrolyte includes co-solvent(s), for example, methanol and/or ethanol.
The method may also include collecting a reduction product from the apparatus. The reduction product may include materials such as, but not limited to, a hydrocarbon, an aldehyde, an alcohol, a ketone, a carboxylic acid, or a mixture of any two or more thereof. The method includes collecting a reduction product that may be ethylene, methane, or a mixture thereof.
In some of the above embodiments, the method may also include monitoring the composition of product(s) using an analytical technique. In another embodiment, the analytical technique is gas chromatography mass spectrometry (GCMS).
In some embodiments the hierarchical nanoporous metal is prepared by dealloying a metal alloy. In another embodiment the hierarchical nanoporous metal is prepared by direct ink writing.
The stability of the hierarchical nanoporous metal against electrochemical potential and reaction conditions may be increased by adding one or more step-edge pinning agent(s) to the hierarchical nanoporous metal. In some embodiments, the step-edge pinning agent(s) are included in a concentration greater than 0 but less than 5% by weight. In some embodiments, the step-edge pinning agent(s) may be added via atomic layer deposition. Step-edge pinning agents may be alumina or titania.
Alternative to, or in addition to the step-edge agent(s), the stability of the hierarchical nanoporous metal against electrochemical potentials and reaction conditions may be increased by doping the metal alloy used to produce the hierarchical nanoporous metal with one or more metals (for example, nickel) having a melting point greater than about 1,500° C.
In any of the above embodiments, flowing includes applying a pressure gradient across the cathode, in a further embodiment the pressure gradient is from about 0.1 atm to about 10 atm. In any of the above embodiments, the electrolyte flows through the cathode at a velocity of less than about 1 cm/s.
In any of the above embodiments, the electrolyte may contain a salt, such as, but not limited to, KH2PO4, K2HPO4, or KHCO3. In any of the above embodiments the KH2PO4, K2HPO4, or KHCO3 may be present in the electrolyte from about 0.1 M to about 5 M. In some embodiments, the electrolyte is saturated with CO2.
In any of the above embodiments the cathode includes one or more of copper, platinum, silver, gold, nickel, iron and zinc. In any of the above embodiments, the anode includes one or more of platinum, palladium, carbon and boron-doped carbon/diamond.
The following examples are intended to illustrate the invention and should not be construed as limiting the invention in any way.
The hierarchical nanoporous copper may be prepared by dealloying an aluminum-copper alloy. An Al—Cu alloy, Al75Cu25, is melted in a horizontal tube furnace at 800° C. under argon for 24 hr at a ramp rate of 5° C./min. This melted alloy is then cooled down and solidified at 2° C./min until reaching room temperature. Dealloying is then accomplished by chemically dealloying the alloy in 1M HCl at 5° C. under vacuum. The Al75Cu25 alloy, after melting and cooling, contains both pre-eutectic Al2Cu and lamellar eutectic α-Al/Al2Cu. If desired, the size of the hnp-Cu channels formed after dealloying are increased by varying the solidification time of molten alloy. This increases the thickness of the Al lamella that define the size of the macroporous flow channels formed during dealloying.
The electrolyte is based upon a KH2PO4/K2HPO4 buffer. The KH2PO4 and K2HPO4 are present at a concentration between 0.1 M to 5 M. The pH value of the solution may be verified on a pH meter calibrated with two standard buffer solutions. The pH range can be between 5 and 12, preferably between 7 and 10. An alternative electrolyte is prepared as a 0.1 M to 5 M KHCO3 solution. CO2 is bubbled through the electrolyte during operation of the flow-through cell to saturate the electrolyte with CO2.
CO2 is reduced using the flow-through electrolysis cell of
While the reduction of CO2 occurs at the cathode, oxidation of water occurs at the metallic mesh anode (18) when the electrolyte is forced into the cell under pressure through electrolyte-in line (14) and bathes the anode. Electrolyte subsequently leaves the cell through electrolyte-out line (15). A steady flow of electrolyte is maintained in this fashion. Electrolyte flowing-through the hierarchical nanoporous metal cathode (17) and electrolyte at the metallic mesh anode (18) are kept from intermixing by the AEM (9).
CO2 is reduced using the flow-through electrolysis cell of
While the reduction of CO2 occurs at the cathode, oxidation of water occurs at the metallic mesh anode (34) when electrolyte is forced into the cell under pressure through electrolyte-in line (32) and bathes the anode. Electrolyte subsequently leaves the cell through electrolyte-out line (33). A steady flow of electrolyte is maintained in this fashion. Electrolyte flowing-through the hierarchical nanoporous metal cathode (36) and electrolyte at the metallic mesh anode (34) are kept from intermixing by the PEM (27).
Morphological and chemical changes to the hnp-Cu electrode occurring during operation of the cell may be monitored using synchrotron-based in-situ scattering, preferably resonant soft x-ray scattering (RSoXS) and spectroscopy. To do so, the cathode is illuminated with x-rays and the scattering of x-rays incident upon the cathode is then monitored spectroscopically.
While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.
The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.
The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.
As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.
All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.
Other embodiments are set forth in the following claims.
The United States Government has rights in the invention pursuant to Contract No. DE-AC52-07NA27344 between the U.S. Department of Energy and Lawrence Livermore National Security, LLC, for the operation of Lawrence Livermore National Laboratory.
