(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2018/071818 Al 19 April 2018 (19.04.2018) W ! P O PCT (51) International Patent Classification: (72) Inventor; and C25B 9/08 (2006.01) C12G 3/04 (2006.01) (71) Applicant: SHEEHAN, Stafford Wheeler [US/US]; 201 C25B 9/18 (2006.01) C12G 3/00 (2006.01) Stoney Hollow Rd., Tiverton, RI 02878 (US). C25B / 0 (2006.01) (74) Agent: ATKINS, Lucas P. et al; Foley Hoag LLP, 155 (21) International Application Number: Seaport Boulevard, Boston, MA 02210-2600 (US). PCT/US2017/056589 (81) Designated States (unless otherwise indicated, for every (22) International Filing Date: kind of national protection available): AE, AG, AL, AM, 13 October 2017 (13.10.2017) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO, (25) Filing Language: English DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, (26) Publication Language: English HR, HU, ID, IL, IN, IR, IS, JO, JP, KE, KG, KH, KN, KP, KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, (30) Priority Data: MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, 62/408,172 14 October 2016 (14.10.2016) US OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, 62/433,828 14 December 2016 (14.12.2016) US SC, SD, SE, SG, SK, SL, SM, ST, SV, SY,TH, TJ, TM, TN, 62/468,676 08 March 20 17 (08.03 .20 17) US TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (54) Title: SYSTEMS AND METHODS FOR VARIABLE PRESSURE ELECTROCHEMICAL CARBON DIOXIDE REDUCTION 200 ~ 0 / ater Qu 202 Fe PT Fittings 30(3/400 Fuei Ceti Piates 214 Steel Pressure Chamber 216 Product Collection P o < F G. 2 00 (57) Abstract: Electrochemical devices, such as membrane electrode assemblies and electrochemical reactors, are described herein, as 00 well as and methods for the conversion of reactants such as carbon dioxide to value-added products such as ethanol. In certain aspects, the membrane electrode assemblies are configured to allow for distributed pressure along the cathodic side of a membrane electrode © assembly is described. The pressure vessel acts as a cathode chamber, both for the feed of reactant carbon dioxide as well as collection of products. The designs described herein improves the safety of high pressure electrochemical carbon dioxide reduction and allows 00 for varied pressures to be used, in order to optimize reaction conditions. Configurations optimized for producing preferred products, o such as ethanol, are also described. [Continued on nextpage] WO 2018/071818 Al llll II II 11III II I II III II II II I III II I II (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG). Published: SYSTEMS AND METHODS FOR VARIABLE PRESSURE ELECTROCHEMICAL CARBON DIOXIDE REDUCTION REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 62/408,172, filed October 14, 2016, U.S. Provisional Application No. 62/433,828, filed December 14, 2016, and U.S. Provisional Application No. 62/468,676, filed March 8, 2017, the contents of each of which are fully incorporated by reference herein in their entireties. BACKGROUND OF THE INVENTION Plants use photosynthesis to convert carbon dioxide, water, and solar energy into chemical energy by creating sugars and other complex hydrocarbons. This effectively stores the energy in absorbed photons from the sun in the chemical bonds of a carbon-based compound. This process has been supporting the Earth's ecosystem and balancing carbon dioxide concentration in our atmosphere for billions of years, and humans use this process to grow crops for food and chemical production. In the last century, human beings have harnessed byproducts of photosynthesis, such as fossil fuels, to provide the energy required for modern life. Since the industrial revolution, human activity has released millions of tons of carbon dioxide into the Earth's atmosphere. To counteract these emissions, researchers have been attempting to find processes that can sequester carbon dioxide into the chemical bonds of carbon-based compounds. However, methods of efficiently transforming carbon dioxide into useful chemicals are still needed. SUMMARY OF THE INVENTION In certain aspects, the present disclosure provides an electrode assembly comprising an anode endplate; a cathode endplate; a polymer electrolyte membrane having a cathodic side and an anodic side disposed between the anode endplate and the cathode endplate; and a cathode catalyst disposed on the cathodic side of the polymer electrolyte membrane; wherein the cathode endplate is configured to allow the cathodic side of the polymer electrolyte membrane to be in fluid communication with a fluid surrounding the electrode assembly In certain aspects, the present disclosure provides an electrochemical reactor, comprising a pressure vessel; an electrode stack comprising one or more electrode assemblies; wherein the cathodic side of the polymer electrolyte membrane is open to the atmosphere of the pressure vessel. In certain aspects, the present disclosure provides a method for electrochemical reduction of carbon dioxide using an electrode assembly or an electrochemical reactor comprising an electrode assemble, comprising supplying a catholyte comprising CO2 to the cathodic side of the polymer electrolyte membrane; supplying an anolyte comprising water to the anodic side of the polymer electrolyte membrane; and applying a voltage between the anode endplate and the cathode endplate, thereby reducing the CO2 to a CO2 reduction product. In certain embodiments, the reduction product comprises ethanol. In certain aspects, the present disclosure provides a method for producing an alcoholic beverage, comprising mixing ethanol produced by the above methods with a beverage ingredient. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a simplified flow diagram for the case of flue gas emissions from a coal-fired power plant in a CO2 reduction process. First, flue gas is purified to remove soot and potential catalyst poisons or membrane fouling agents. It is then fed into the cathode chamber of an electrochemical system, where it is combined with protons supplied via the water oxidation half reaction and electrons from a DC power source to form the products. Figure 2 shows one embodiment of an exemplary electrochemical system of the present disclosure, which includes an MEA stack with cathodes open to the pressure vessel and an anode feed that is not open to the pressure vessel. Carbon dioxide under high pressure is flowed into the cathode chamber, and may be moistened to assist membrane hydration and product formation at the MEAs. Variable temperature at the stacks (due to overpotential heat loss) and at the bottom of the pressure vessel allow for product collection. Figure 3 shows the internal configuration of an individual MEA in an electrolyzer stack or electrolysis unit, showing individual components and how the feed reactants (water from the anode feed and moistened carbon dioxide from the cathode feed) can be transported to the anode and cathode gas diffusion layers and electrodes of the membrane electrode assembly by directed flow. The flow field patterns may be any pattern that maximizes contact between the anolyte (water) or catholyte (carbon dioxide) and the membrane electrode assembly and allows for transportation of products (oxygen gas, ethanol, and other byproducts) out of the system, such as a serpentine pattern or a parallel pattern. Figure 4 shows the internal configuration of an electrolysis unit in which the cathode side of the membrane is open to the atmosphere of the pressure vessel. The channels in the cathode endplate are open to allow CO2 to reach the membrane by diffusion, or by flowing through the channels at a very low pressure drop, as could be caused by a 75 low-power fan. Figure 5 shows an external view of an exemplary reactor that uses high pressure carbon dioxide as a reactant to produce ethanol. Figure 6 shows an external view of the lid of an exemplary reactor, where the reactants carbon dioxide and water are fed in and positive and negative terminals for the 80 cathode and anode are provided for connection with a DC power source. Figure 7 shows a view of the inside of an exemplary reactor, which contains an electrolysis unit having the internal configuration depicted in Figure 4 and an outlet through with ethanol product can be collected. Figure 8 shows the peripheral systems around the reactor that support the high 85 pressures on either side of the membrane. Carbon dioxide is fed directly into the system, while water is recirculated in an external loop to ensure consistent pressure across the anode flow plate. DETAILED DESCRIPTION OF THE INVENTION The present disclosure provides apparatus and methods for reducing carbon dioxide 90 to carbon dioxide reduction products. In general form, the reaction that takes place is: → xC02 +y 20 Products + z02 Where x, y, z are stoichiometric coefficients and are dependent on the products being made by the carbon dioxide reduction reaction. Common products of this reaction include, but are not limited to, CO, HCO2H, HCHO, CH3OH, CH4, CH3CH2OH, CH3CH3.