Champaign, IL, United States
Champaign, IL, United States

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An electrochemical device converts carbon dioxide to a formic acid reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each have reactant introduced thereto. Two membranes, a cation exchange polymer electrolyte membrane and an anion exchange polymer electrolyte membrane, are interposed between the anode and the cathode, forming a central flow compartment where a carbon dioxide reduction product, such as formic acid, can be recovered. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm^(2), measured as the area of the cathode gas diffusion layer that is covered by catalyst, and formate ion selectivity is at least 50% at a cell potential difference of 3.0 V. In some embodiments, at least one polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.


Patent
Dioxide Materials Inc | Date: 2017-01-06

An anion-conducting polymeric membrane comprises a terpolymer of styrene, vinylbenzyl-R_(s )and vinylbenzyl-R_(x). R_(s )is a positively charged cyclic amine group. R_(x )is at least one constituent selected from the group consisting Cl, OH and a reaction product between an OH or Cl and a species other than a simple amine or a cyclic amine. The total weight of the vinylbenzyl-R_(x )groups is greater than 0.3% of the total weight of the membrane. In a preferred embodiment, the membrane is a Helper Membrane that increases the faradaic efficiency of an electrochemical cell into which the membrane is incorporated, and also allows product formation at lower voltages than in cells without the Helper Membrane.


Grant
Agency: Department of Energy | Branch: | Program: STTR | Phase: Phase I | Award Amount: 150.00K | Year: 2016

The objective of the proposed work is to develop, demonstrate, and evaluate new technologies for low-cost, high-accuracy, whole-building CO2 monitoring for demand control ventilation. The work builds on a private/public partnership formed between Dioxide MaterialsTM and the Institute for Sensing and Embedded Network Systems Engineering (I-SENSE) at Florida Atlantic University. In previous, NSF-supported work, Dioxide MaterialsTM has developed low-cost, low-power CO2 sensors for building HVAC applications. The sensors show better signal-to-noise than commercially available sensors and cost an order of magnitude less to manufacture. I-SENSE is a leader in the design and application of low-cost, low-power telemetry platforms and sensor network systems. Together, the team will develop the electronics and software necessary to interface Dioxide MaterialsTM’s sensors to a building DDC system. In particular, the project will concentrate on developing a wireless networking platform and associated firmware to provide signal conditioning and conversion, fault- and disruption-tolerant networking, and multi-hop routing at building scales to avoid rewiring costs. If successful, the public benefits could be profound: The devices and resulting system will lower the amount of energy homes and businesses use for heating, ventilating, and air conditioning (HVAC), resulting in significant savings for everyone in America. This will be accomplished by changing the controls in the HVAC system to use less energy by using CO2 sensors to measure air quality and occupancy of each room, and adjusting the HVAC systems accordingly. The U.S. DOE website for information on Energy Efficiency and Renewable Energy (EERE) claims that demand control ventilation using CO2 sensors could reduce the energy costs of heating and cooling of a building by 10-30%. Key Words: Carbon dioxide sensing, demand control ventilation, HVAC efficiency / energy savings, wireless sensor networking


Patent
Dioxide Materials Inc | Date: 2016-05-06

Electrochemical sensors measure an amount or concentration of CO_(2), typically using catalysts that include at least one Catalytically Active Element and one Helper Catalyst. The catalysts can be used to increase the rate, modify the selectivity or lower the overpotential of chemical reactions. These catalysts are useful for a variety of chemical reactions including electrochemical conversion of CO_(2). Chemical processes and devices employing the catalysts are also disclosed, including processes that produce CO, OH^(), HCO^(), H_(2)CO, (HCO_(2))^(), H_(2)CO_(2), CH_(3)OH, CH_(4), C_(2)H_(4), CH_(3)CH_(2)OH, CH_(3)COO^(), CH_(3)COOH, C_(2)H_(6), O_(2), H_(2), (COOH)_(2), and (COO^())_(2).


Patent
Dioxide Materials Inc | Date: 2016-08-02

Electrochemical devices comprising electrocatalyst mixtures include at least one Catalytically Active Element and, as a separate constituent, one Helper Catalyst. The electrocatalysts can be used to increase the rate, modify the selectivity or lower the overpotential of chemical reactions. These electrocatalysts are useful for a variety of chemical reactions including, in particular, the electrochemical conversion of CO_(2). Chemical processes employing these catalysts produce CO, HCO^(), H_(2)CO, (HCO_(2))^(), H_(2)CO_(2), CH_(3)OH, CH_(4), C_(2)H_(4), CH_(3)CH_(2)OH, CH_(3)COO^(), CH_(3)COOH, C_(2)H_(6), (COOH)_(2), or (COO^())_(2). Devices using the electrocatalysts include, for example, a CO_(2 )sensor and a CO_(2 )electrolyzer.


Grant
Agency: Department of Commerce | Branch: National Oceanic and Atmospheric Administration | Program: SBIR | Phase: Phase II | Award Amount: 400.00K | Year: 2015

The objective of the proposed work is to create low cost, low power sensors for autonomous measurement of ocean carbon. In our Phase I effort, we showed that Dioxide Materials’ miniature CO2 sensors have the speed and sensitivity to meet NOAA’s requirements for sensing ocean carbon. The objective of the proposed work is to further develop the sensors so that they can be used directly in NOAA’s existing ocean carbon measurement system. Work incudes temperature compensation, so the devices can work in the Arctic, interface changes so the devices can communicate with NOAA’s existing hardware, and other changes. At the end of the program we propose doing a field test at NOAA’s location so we can verify performance for the intended application.


Patent
Dioxide Materials Inc | Date: 2016-04-04

An ion conducting polymeric composition mixture comprises a copolymer of styrene and vinylbenzyl-R_(s). R_(s )is selected from the group consisting of imidazoliums, pyridiniums, pyrazoliums, pyrrolidiniums, pyrroliums, pyrimidiums, piperidiniums, indoliums, and triaziniums. The composition contains 10%-90% by weight of vinylbenzyl-R_(s). The composition can further comprise a polyolefin comprising substituted polyolefins, a polymer comprising cyclic amine groups, a polymer comprising at least one of a phenylene group and a phenyl group, a polyamide, and/or the reaction product of a constituent having two carbon-carbon double bonds. The composition can be in the form of a membrane. In a preferred embodiment, the membrane is a Helper Membrane that increases the faradaic efficiency of an electrochemical cell into which the membrane is incorporated, and also allows product formation at lower voltages than in cells without the Helper Membrane.


Patent
Dioxide Materials Inc | Date: 2016-05-18

A catalyst layer for an electrochemical device comprises a catalytically active element and an ion conducting polymer. The ion conducting polymer comprises positively charged cyclic amine groups. The ion conducting polymer comprises at least one of an imidazolium, a pyridinium, a pyrazolium, a pyrrolidinium, a pyrrolium, a pyrimidium, a piperidinium, an indolium, a triazinium, and polymers thereof. The catalytically active element comprises at least one of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce and Nd. In an electrolyzer comprising the present catalyst layer, the feed to the electrolyzer comprises at least one of CO_(2 )and H_(2)O.


Grant
Agency: Department of Energy | Branch: | Program: SBIR | Phase: Phase I | Award Amount: 150.00K | Year: 2016

The objective of the proposed work is to develop a novel process for the conversion of CO2, water and renewable energy into transportation fuels. The work will combine the efforts of two companies: Dioxide Materials™, experts on using renewable energy (electricity) to convert CO2 and water into syngas; and Primus Green Energy, experts on converting syngas to gasoline. First, Dioxide Materials™’ patented electrochemical process will be used to convert CO2 to CO (and O2) with renewable electricity as an input. 3M’s patented electrochemical process will be used to create hydrogen. Then the mixture of CO and H2 (i.e., syngas) will be sent to Primus Green Energy’s patented process to produce gasoline. In Phase I, we will develop technology to scale Dioxide Materials™’s electrolyzers, and plan for a unit that combines the efforts of the three companies. If we are successful, we will have developed an economic way to convert CO2 into a viable transportation fuel using renewable energy. This advance will have several public benefits: - It reduces CO2 emissions. - The process will provide a viable route to renewable fuels that does not compete with the food supply. Biofuels have been nice additions to the U.S. fuel mix, but they compete with food production for land and water. This project can provide a source of renewable fuels that does not compete with the food supply. - It will provide a route to store renewable energy when it is produced, allowing intermittent renewable energy sources such as sun or wind to more easily interface to the grid. Key Words: Carbon Dioxide Utilization, Technology to combat climate change, renewable gasoline, synthetic fuels


Grant
Agency: Department of Energy | Branch: | Program: SBIR | Phase: Phase II | Award Amount: 1.01M | Year: 2014

The objective of this project is to develop and energy efficient method to convert CO2 and water to formic acid. Formic acid is widely used in Europe as an alternative to antibiotics in animal feed, and for grain preservation, but it has not been adapted in the US because it is more expensive than other alternatives. The objective of Dioxide Materials work is to make formic acid from a carbon dioxide feedstock, at a cost less than antibiotics or other alternatives and take advantage of the fact that formic acid is generally recognized as safe for human consumption. Key advantages of the work include: 1) Carbon dioxide, that is now a waste product contributing to global warming, will change to a valuable feedstock to produce useful chemicals; 2) farmers will have an economic incentive to switch from antibiotics to formic acid. That will save farmers money and at the same time lead to healthier foods with no residual antibiotics. In our previous Phase II effort, Catalysis of CO2 Conversion into Useful Chemicals, we developed catalysts that could convert CO2 to useful chemicals at high energy efficiency. The effort was tremendously successful. We lowered the energy needed to produce the products by a factor of 2. The work was published in Science and has appeared in over 200 news articles. The objective of the work proposed in this proposal is to move from an efficient catalyst for production of formic acid to a complete system for the production of the formic acid. The system will include all of the parts of the electrolyzer: the cell itself, the membrane, and the anode. It will also include the separation system to purify the product. Our goal is to lower the cost of formic acid by a factor of 2 or more to prices lower than antibiotics or other food preservatives or even of methanol.

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