Dioxide Materials

Last updated
Dioxide Materials
Company typePrivate
Industry Chemical industry
Genre Carbon capture and storage, Ion-exchange membranes
FoundedSeptember 9, 2009;14 years ago (2009-09-09) in Champaign, Illinois, US
Headquarters
Boca Raton, Florida
,
US
ProductsSustainion Alkaline Ionomers and Alkaline Ion Exchange Membranes, Carbon Dioxide and Water Electrolyzers
Website dioxidematerials.com

Dioxide Materials was founded in 2009 in Champaign, Illinois, and is now headquartered in Boca Raton, Florida. Its main business is to develop technology to lower the world's carbon footprint. Dioxide Materials is developing technology to convert carbon dioxide, water and renewable energy into carbon-neutral gasoline (petrol) or jet fuel. Applications include CO2 recycling, [1] sustainable fuels production [1] and reducing curtailment of renewable energy [2] [3] (i.e. renewable energy that could not be used by the grid [2] ).

Contents

Carbon Dioxide Electrolyzer Technology

Carbon Dioxide electrolyzers are a major part of Dioxide Materials' business. [4] The work started in response to a Department of Energy challenge to find better catalysts for electrochemical reduction of carbon dioxide. [5] At the time the overpotential (i.e. wasted voltage) was too high, and the rate too low for practical applications. [5] [6] Workers at Dioxide Materials theorized that a bifunctional catalyst consisting of a metal and an ionic liquid might lower the overpotential for electrochemical reduction of carbon dioxide. Indeed, it was found that the combination of two catalysts, silver nanoparticles and an ionic liquid solution containing equal volumes of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) and water, reduced the overpotential for CO2 conversion to carbon monoxide (CO) from about 1 volt to only 0.17 volts. [7] Workers from other laboratories have subsequently reproduced the findings on many metals, and with several ionic liquids. [8] Dioxide Materials has shown that a similar enhancement occurs during alkaline water electrolysis [9] [10] and the hydrocarboxylation of acetylene [11] ("Reppe chemistry").

Dioxide Materials' proposed reaction pathway for CO2 electrolysis on silver in the presence (green) and absence (black) of EMIM CO2 electrolysis pathway.png
Dioxide Materials' proposed reaction pathway for CO2 electrolysis on silver in the presence (green) and absence (black) of EMIM

At this point, there is still some question about how the imidazolium is able to lower the overpotential for the electrochemical reduction of carbon dioxide. The first step in the electrolysis of CO2 is the addition of an electron into the CO2 or a molecular complex containing CO2. The resultant species is labeled "CO2¯" in the figure on the left. It requires at least an electron-volt of energy per molecule to form the species in the absence of the ionic liquid. [12] That electron-volt of energy is largely wasted during the reaction. Rosen at al [7] postulated that a new complex forms in presence of the ionic liquid so that 1 eV of energy is not wasted. The complex allows the reaction to follow the green pathway on the figure on the right. Recent work suggests that the new complex is a zwitterion [13] Other possible pathways (i.e. non-zwitterions) are discussed in Keith et al. [14] Rosen at al. [15] Verdaguer-Casadevall et al. [16] and Shi et al. [17]

Sustainion Membranes

The structure of Sustainion 37 Sustainion 37 labeled.png
The structure of Sustainion 37

Unfortunately, ionic liquids were found to be too corrosive to be used in practical carbon dioxide electrolyzers. Ionic liquids are strong solvents. They dissolve/corrode the seals, carbon electrodes and other parts in commercial electrolyzers. As a result, they were difficult to be used in practice.

In order to avoid the corrosion, Dioxide Materials switched from ionic liquid catalysts to catalytic anion exchange polymers. [18] [19] A number of polymers were tested and the imidazolium functionalized styrene polymer shown in the figure on the right showed the best performance. [18] [20] The membranes were tradenamed Sustainion. The use of Sustainion membranes raised the current and lifetime of the CO2 electrolyzer into the commercially useful range. [21] [22] [23] [24] [25] Sustainion membranes have shown conductivities above 100 mS/cm under alkaline conditions at 60 °C, [10] stability for thousands of hours in 1M KOH, [10] and offer a physical mechanical stability that is useful for many different applications. The membranes showed a lifetime over 3000 hours in CO2 electrolyzers at high current densities. [26] [10] More recent research has noted that a cell membrane that has an optimized cathode has the capability of running for up to 158 days at 200 mA/cm2 . [27]

Related Research Articles

<span class="mw-page-title-main">Fuel cell</span> Device that converts the chemical energy from a fuel into electricity

A fuel cell is an electrochemical cell that converts the chemical energy of a fuel and an oxidizing agent into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requiring a continuous source of fuel and oxygen to sustain the chemical reaction, whereas in a battery the chemical energy usually comes from substances that are already present in the battery. Fuel cells can produce electricity continuously for as long as fuel and oxygen are supplied.

<span class="mw-page-title-main">Electrolysis</span> Technique in chemistry and manufacturing

In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity."

<span class="mw-page-title-main">Proton-exchange membrane fuel cell</span> Power generation technology

Proton-exchange membrane fuel cells (PEMFC), also known as polymer electrolyte membrane (PEM) fuel cells, are a type of fuel cell being developed mainly for transport applications, as well as for stationary fuel-cell applications and portable fuel-cell applications. Their distinguishing features include lower temperature/pressure ranges and a special proton-conducting polymer electrolyte membrane. PEMFCs generate electricity and operate on the opposite principle to PEM electrolysis, which consumes electricity. They are a leading candidate to replace the aging alkaline fuel-cell technology, which was used in the Space Shuttle.

<span class="mw-page-title-main">Ionic liquid</span> Salt in the liquid state

An ionic liquid (IL) is a salt in the liquid state at ambient conditions. In some contexts, the term has been restricted to salts whose melting point is below a specific temperature, such as 100 °C (212 °F). While ordinary liquids such as water and gasoline are predominantly made of electrically neutral molecules, ionic liquids are largely made of ions. These substances are variously called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.

A proton-exchange membrane, or polymer-electrolyte membrane (PEM), is a semipermeable membrane generally made from ionomers and designed to conduct protons while acting as an electronic insulator and reactant barrier, e.g. to oxygen and hydrogen gas. This is their essential function when incorporated into a membrane electrode assembly (MEA) of a proton-exchange membrane fuel cell or of a proton-exchange membrane electrolyser: separation of reactants and transport of protons while blocking a direct electronic pathway through the membrane.

<span class="mw-page-title-main">Electrolysis of water</span> Electricity-induced chemical reaction

Electrolysis of water is using electricity to split water into oxygen and hydrogen gas by electrolysis. Hydrogen gas released in this way can be used as hydrogen fuel, but must be kept apart from the oxygen as the mixture would be extremely explosive. Separately pressurised into convenient 'tanks' or 'gas bottles', hydrogen can be used for oxyhydrogen welding and other applications, as the hydrogen / oxygen flame can reach approximately 2,800°C.

Formic acid fuel cells (direct formic acid fuel cells or DFAFCs) are a subcategory of direct liquid-feed fuel cells (DLFCs), in which the liquid fuel is directly oxidized (electrochemically) at the anode instead of reforming to produce hydrogen. Formic acid-based fuel cells represent a promising energy supply system in terms of high volumetric energy density, theoretical energy efficiency, and theoretical open-circuit voltage. They are also able to overcome certain problems inherent to traditional hydrogen (H2) feed fuel cells such as safe handling, storage, and H2 transportation.

Hydrogen purification is any technology used to purify hydrogen. The impurities in hydrogen gas depend on the source of the H2, e.g., petroleum, coal, electrolysis, etc. The required purity is determined by the applicatoin of the hydrogne gas. For example, ultra-high purified hydrogen is needed for applications like proton exchange membrane fuel cells.

<span class="mw-page-title-main">Electrocatalyst</span> Catalyst participating in electrochemical reactions

An electrocatalyst is a catalyst that participates in electrochemical reactions. Electrocatalysts are a specific form of catalysts that function at electrode surfaces or, most commonly, may be the electrode surface itself. An electrocatalyst can be heterogeneous such as a platinized electrode. Homogeneous electrocatalysts, which are soluble, assist in transferring electrons between the electrode and reactants, and/or facilitate an intermediate chemical transformation described by an overall half reaction. Major challenges in electrocatalysts focus on fuel cells.

The electrochemical reduction of carbon dioxide, also known as CO2RR, is the conversion of carbon dioxide to more reduced chemical species using electrical energy. It represents one potential step in the broad scheme of carbon capture and utilization.

The lithium–air battery (Li–air) is a metal–air electrochemical cell or battery chemistry that uses oxidation of lithium at the anode and reduction of oxygen at the cathode to induce a current flow.

Photoelectrochemical reduction of carbon dioxide, also known as photoelectrolysis of carbon dioxide, is a chemical process whereby carbon dioxide is reduced to carbon monoxide or hydrocarbons by the energy of incident light. This process requires catalysts, most of which are semiconducting materials. The feasibility of this chemical reaction was first theorised by Giacomo Luigi Ciamician, an Italian photochemist. Already in 1912 he stated that "[b]y using suitable catalyzers, it should be possible to transform the mixture of water and carbon dioxide into oxygen and methane, or to cause other endo-energetic processes."

Water oxidation is one of the half reactions of water splitting:

<span class="mw-page-title-main">Alkaline anion-exchange membrane fuel cell</span>

An alkaline anion-exchange membrane fuel cell (AAEMFC), also known as anion-exchange membrane fuel cells (AEMFCs), alkaline membrane fuel cells (AMFCs), hydroxide-exchange membrane fuel cells (HEMFCs), or solid alkaline fuel cells (SAFCs) is a type of alkaline fuel cell that uses an anion-exchange membrane to separate the anode and cathode compartments.

A solar fuel is a synthetic chemical fuel produced from solar energy. Solar fuels can be produced through photochemical, photobiological, and electrochemical reactions.

<span class="mw-page-title-main">Proton exchange membrane electrolysis</span> Technology for splitting water molecules

Proton exchange membrane(PEM) electrolysis is the electrolysis of water in a cell equipped with a solid polymer electrolyte (SPE) that is responsible for the conduction of protons, separation of product gases, and electrical insulation of the electrodes. The PEM electrolyzer was introduced to overcome the issues of partial load, low current density, and low pressure operation currently plaguing the alkaline electrolyzer. It involves a proton-exchange membrane.

Karen Chan is an associate professor at the Technical University of Denmark. She is a Canadian and French physicist most notable for her work on catalysis, electrocatalysis, and electrochemical reduction of carbon dioxide.

The Bionic Leaf is a biomimetic system that gathers solar energy via photovoltaic cells that can be stored or used in a number of different functions. Bionic leaves can be composed of both synthetic and organic materials (bacteria), or solely made of synthetic materials. The Bionic Leaf has the potential to be implemented in communities, such as urbanized areas to provide clean air as well as providing needed clean energy.

Hydrogen evolution reaction (HER) is a chemical reaction that yields H2. The conversion of protons to H2 requires reducing equivalents and usually a catalyst. In nature, HER is catalyzed by hydrogenase enzymes. Commercial electrolyzers typically employ platinum supported as the catalyst at the anode of the electrolyzer. HER is useful for producing hydrogen gas, providing a clean-burning fuel. HER, however, can also be an unwelcome side reaction that competes with other reductions such as nitrogen fixation, or electrochemical reduction of carbon dioxide or chrome plating.

<span class="mw-page-title-main">Anion exchange membrane electrolysis</span> Splitting of water using a semipermeable membrane

Anion exchange membrane(AEM) electrolysis is the electrolysis of water that utilises a semipermeable membrane that conducts hydroxide ions (OH−) called an anion exchange membrane. Like a proton-exchange membrane (PEM), the membrane separates the products, provides electrical insulation between electrodes, and conducts ions. Unlike PEM, AEM conducts hydroxide ions. The major advantage of AEM water electrolysis is that a high-cost noble metal catalyst is not required, low-cost transition metal catalyst can be used instead. AEM electrolysis is similar to alkaline water electrolysis, which uses a non-ion-selective separator instead of an anion-exchange membrane.

References

  1. 1 2 ARPA-E Brief: Converting CO2 Into Fuels and Chemicals  
  2. 1 2 Lori Bird, Jaquelin Cochran, and Xi Wang, Wind and Solar Energy Curtailment: Experience and Practices in the United States, NREL Report NREL/TP-6A20-60983, March 2014  
  3. ↑ ARPA-E Brief: High Efficiency Hydrogen Production  
  4. ↑ Dioxide Materials website
  5. 1 2 A. Bell et al. Basic research needs catalysts for energy, DOE PNNL-17214  
  6. ↑ Halmann and Steinberg, "Greenhouse Gas Carbon Dioxide Mitigation," Lewis Publishers, 1999. ISBN   1-56670-284-4
  7. 1 2 Brian A. Rosen, Amin Salehi-Khojin, Michael R. Thorson, W. Zhu, Devin T. Whipple, Paul J. A. Kenis, Richard I Masel *, Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials, Science Vol. 334 no. 6056 pp. 643-644 (2011) doi : 10.1126/science.1209786.
  8. ↑ Citations for Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials  
  9. ↑ R. I. Masel, Z. Liu, and S. D. Sajjad Anion Exchange Membrane Electrolyzers Showing 1 A/cm2 at Less Than 2 V, ECS Transactions, 75 (14) 1143-1146 (2016) doi : 10.1149/07514.1143ecst
  10. 1 2 3 4 Zengcai Liu, Syed Dawar Sajjad, Yan Gao, HongzhouYang. Jerry J.Kaczur. Richard I.Masel, The effect of membrane on an alkaline water electrolyzer, International Journal of Hydrogen Energy 42(50), 29661-29665 (2017) doi : 10.1016/j.ijhydene.2017.10.050
  11. ↑ Richard I. Masel, Zheng Richard Ni, Qingmei CHEN, Brian A. Rosen, Process for the sustainable production of acrylic acid, US Patent 9790161
  12. ↑ Chemistry Views (Elsevier) Converting CO2 with Less Energy  
  13. ↑ Mark Pellerite, Marina Kaplun, Claire Hartmann-Thompson, Krzysztof A. Lewinski, Nancy Kunz, Travis Gregar, John Baetzold, Dale Lutz, Matthew Quast, Zengcai Liu, Hongzhou Yang, Syed D. Sajjad, Yan Gao, and Rich Masel Imidazolium-Functionalized Polymer Membranes for Fuel Cells and Electrolyzers, ECS Trans. 2017 80(8): 945-956; doi : 10.1149/08008.0945ecst
  14. ↑ John A. Keith and Emily A. Carter, Theoretical Insights into Electrochemical CO2 Reduction Mechanisms Catalyzed by Surface-Bound Nitrogen Heterocycles, J. Phys. Chem. Lett., 2013, 4 (23), pp 4058–4063 doi : 10.1021/jz4021519
  15. ↑ Jonathan Rosen, Gregory S. Hutchings, Qi Lu, Sean Rivera, Yang Zhou, Dionisios G. Vlachos, and Feng Jiao, Mechanistic Insights into the Electrochemical Reduction of CO2 to CO on Nanostructured Ag Surfaces, ACS Catal., 2015, 5 (7), pp 4293–4299 doi : 10.1021/acscatal.5b00840
  16. ↑ Arnau Verdaguer-Casadevall, Christina W. Li‡, Tobias P. Johansson, Soren B. Scott, Joseph T. McKeown, Mukul Kumar, Ifan E. L. Stephens, Matthew W. Kanan*, and Ib Chorkendorff* Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts, J. Am. Chem. Soc., 2015, 137 (31), pp 9808–9811 doi : 10.1021/jacs.5b06227
  17. ↑ Chuan Shi, Heine A. Hansen, Adam C. Lauscheb, and Jens K. Nørskov, Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces, Phys. Chem. Chem. Phys., 2014,16, 4720-4727 doi : 10.1039/C3CP54822H
  18. 1 2 R. I. Masel, Qingmei Chen, Zengcai liu, Robert Kutz, Ion Conducting Polymers, US patent 9580824  
  19. ↑ Richard I. Masel, Amin Salehi-Khojin, Robert Kutz, Electrocatalytic process for carbon dioxide conversion, US Patent 981501  
  20. ↑ Robert Brian Kutz, Qingmei Chen, Hongzhou Yang, Syed Dawar Sajjad, Zengcai Liu, Richard Masel, Sustainion Imidazolium-functionalized Polymers for Carbon Dioxide Electrolysis, Energy Technology 5, (6) 929-936 (2017) doi : 10.1002/ente.201600636
  21. ↑ R.F. Service, Two new ways to turn ‘garbage’ carbon dioxide into fuel Science, Sept 1, 2017  
  22. ↑ Steven K Ritter, CO2 Electrolyzer Nears Commercialization, C&E News, Volume 93 Issue 13 | p. 30 . March 30, 2015  
  23. ↑ Mark Harris, The entrepreneurs turning carbon dioxide into fuels, The Guardian, 14 Sept 2017  
  24. ↑ SAVVY: Turning Carbon Dioxide into products New Straitus Times, Dec 3, 2017.  
  25. ↑ Michael Foertsch, These methods turn CO2 into cheap energy, Wired, Sept 24, 2017  
  26. ↑ Syed D. Sajjad, Yan Gao, Zengcai Liu, Hongzhou Yang and Rich Masel Tunable-High Performance Sustainion™ Anion Exchange Membranes for Electrochemical Applications ECS Transactions, 77(11): 1653-1656 (2017) doi : 10.1149/07711.1653ecst
  27. ↑ Zengcai Liu et al 2018 J. Electrochem. Soc. 165 J3371 DOI 10.1149/2.0501815jes
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