Dioxide Materials

{{Short description|Chemical company in Boca Raton - Florida, United States}} {{COI|date=April 2018}} {{Infobox company | name = Dioxide Materials | logo = 100px|center|Dioxide Materials logo | type = Private | industry = Chemical industry | genre = Carbon capture and storage, Ion-exchange membranes | founded = {{Start date and age|2009|09|09}} in Champaign, Illinois, US | hq_location_city = Boca Raton, Florida | hq_location_country = US | products = Sustainion Alkaline Ionomers and Alkaline Ion Exchange Membranes, Carbon Dioxide and Water Electrolyzers | website = {{URL|https://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,<ref name = ccc>ARPA-E Brief: ''[https://arpa-e.energy.gov/?q=slick-sheet-project/converting-co2-fuel-and-chemicals Converting CO₂ Into Fuels and Chemicals]''</ref> sustainable fuels production <ref name = ccc /> and reducing curtailment of renewable energy<ref name=curt>Lori Bird, Jaquelin Cochran, and Xi Wang, ''[https://www.nrel.gov/docs/fy14osti/60983.pdf Wind and Solar Energy Curtailment: Experience and Practices in the United States]'', NREL Report NREL/TP-6A20-60983, March 2014</ref><ref>ARPA-E Brief: ''[https://arpa-e.energy.gov/?q=slick-sheet-project/high-efficiency-hydrogen-production-0 High Efficiency Hydrogen Production]''</ref>(i.e. renewable energy that could not be used by the grid<ref name=curt />).

== Carbon Dioxide Electrolyzer Technology == Carbon Dioxide electrolyzers are a major part of Dioxide Materials' business.<ref>[https://dioxidematerials.com Dioxide Materials website]</ref> The work started in response to a Department of Energy challenge to find better catalysts for electrochemical reduction of carbon dioxide.<ref name=bell>A. Bell et al. "[https://www.pnnl.gov/science/images/highlights/cmsd/cat_rpt_print.pdf Basic research needs catalysts for energy]", DOE PNNL-17214</ref> At the time the overpotential (i.e. wasted voltage) was too high, and the rate too low for practical applications.<ref name=bell /><ref>Halmann and Steinberg, "Greenhouse Gas Carbon Dioxide Mitigation," Lewis Publishers, 1999. {{ISBN|1-56670-284-4}}</ref> 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.<ref name=rosen>{{cite journal | last1=Rosen | first1=Brian A. | last2=Salehi-Khojin | first2=Amin | last3=Thorson | first3=Michael R. | last4=Zhu | first4=Wei | last5=Whipple | first5=Devin T. | last6=Kenis | first6=Paul J. A. | last7=Masel | first7=Richard I. | title=Ionic Liquid–Mediated Selective Conversion of CO₂ to CO at Low Overpotentials | journal=Science | date=2011 | volume=334 | issue=6056 | pages=643–644 | doi=10.1126/science.1209786 | pmid=21960532 | bibcode=2011Sci...334..643R }}</ref> Workers from other laboratories have subsequently reproduced the findings on many metals, and with several ionic liquids.<ref>Citations for ''Ionic Liquid-Mediated Selective Conversion of CO₂ to CO at Low Overpotentials'' [https://scholar.google.com/scholar?oi=bibs&hl=en&cites=13981080967619623958&as_sdt=5]</ref> Dioxide Materials has shown that a similar enhancement occurs during alkaline water electrolysis<ref>{{cite journal | last1=Masel | first1=Richard I. | last2=Liu | first2=Zengcai | last3=Sajjad | first3=Syed | title=Anion Exchange Membrane Electrolyzers Showing 1 A/cm² at Less Than 2 V | journal=ECS Transactions | date=2016 | volume=75 | issue=14 | pages=1143–1146 | doi=10.1149/07514.1143ecst | bibcode=2016ECSTr..75n1143M }}</ref><ref name=AW>{{doi |10.1016/j.ijhydene.2017.10.050}}</ref> and the hydrocarboxylation of acetylene <ref>Richard I. Masel, Zheng Richard Ni, Qingmei CHEN, Brian A. Rosen, ''Process for the sustainable production of acrylic acid'', US Patent 9790161 [https://patents.google.com/patent/US9790161]</ref> ("Reppe chemistry").

thumb|left| Dioxide Materials' proposed reaction pathway for CO₂ electrolysis on silver in the presence (green) and absence (black) of EMIMAt 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.<ref name=chemview>{{cite web | title=Converting CO₂ with Less Energy |website=ChemistryViews | date=13 October 2011 | url=https://www.chemistryviews.org/details/news/1362657/Converting_CO2_with_Less_Energy/ }}</ref> That electron-volt of energy is largely wasted during the reaction. Rosen at al<ref name=rosen /> 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<ref>{{cite journal | last1=Pellerite | first1=Mark | last2=Kaplun | first2=Marina | last3=Hartmann-Thompson | first3=Claire | last4=Lewinski | first4=Krzysztof A. | last5=Kunz | first5=Nancy | last6=Gregar | first6=Travis | last7=Baetzold | first7=John | last8=Lutz | first8=Dale | last9=Quast | first9=Matthew | last10=Liu | first10=Zengcai | last11=Yang | first11=Hongzhou | last12=Sajjad | first12=Syed D. | last13=Gao | first13=Yan | last14=Masel | first14=Rich | title=Imidazolium-Functionalized Polymer Membranes for Fuel Cells and Electrolyzers | journal=ECS Transactions | date=2017 | volume=80 | issue=8 | pages=945–956 | doi=10.1149/08008.0945ecst | bibcode=2017ECSTr..80h.945P }}</ref> Other possible pathways (i.e. non-zwitterions) are discussed in Keith et al.<ref>{{cite journal | last1=Keith | first1=John A. | last2=Carter | first2=Emily A. | title=Theoretical Insights into Electrochemical CO₂ Reduction Mechanisms Catalyzed by Surface-Bound Nitrogen Heterocycles | journal=The Journal of Physical Chemistry Letters | date=2013 | volume=4 | issue=23 | pages=4058–4063 | doi=10.1021/jz4021519 }}</ref> Rosen at al.<ref>{{cite journal | last1=Rosen | first1=Jonathan | last2=Hutchings | first2=Gregory S. | last3=Lu | first3=Qi | last4=Rivera | first4=Sean | last5=Zhou | first5=Yang | last6=Vlachos | first6=Dionisios G. | last7=Jiao | first7=Feng | title=Mechanistic Insights into the Electrochemical Reduction of CO₂ to CO on Nanostructured Ag Surfaces | journal=ACS Catalysis | date=2015 | volume=5 | issue=7 | pages=4293–4299 | doi=10.1021/acscatal.5b00840 }}</ref> Verdaguer-Casadevall et al.<ref>{{cite journal | last1=Verdaguer-Casadevall | first1=Arnau | last2=Li | first2=Christina W. | last3=Johansson | first3=Tobias P. | last4=Scott | first4=Soren B. | last5=McKeown | first5=Joseph T. | last6=Kumar | first6=Mukul | last7=Stephens | first7=Ifan E. L. | last8=Kanan | first8=Matthew W. | last9=Chorkendorff | first9=Ib | title=Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts | journal=Journal of the American Chemical Society | date=2015 | volume=137 | issue=31 | pages=9808–9811 | doi=10.1021/jacs.5b06227 | pmid=26196863 | bibcode=2015JAChS.137.9808V | osti=1234582 }}</ref> and Shi et al.<ref>{{cite journal | last1=Shi | first1=Chuan | last2=Hansen | first2=Heine A. | last3=Lausche | first3=Adam C. | last4=Nørskov | first4=Jens K. | title=Trends in electrochemical CO₂ reduction activity for open and close-packed metal surfaces | journal=Physical Chemistry Chemical Physics | date=2014 | volume=16 | issue=10 | pages=4720–4727 | doi=10.1039/C3CP54822H | pmid=24468980 | bibcode=2014PCCP...16.4720S }}</ref>

== Sustainion Membranes == thumb|right|The structure of Sustainion 37Unfortunately, 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.<ref name=sus>R. I. Masel, Qingmei Chen, Zengcai liu, Robert Kutz, ''[https://patents.google.com/patent/US9580824B2 Ion Conducting Polymers]'', US patent 9580824</ref><ref>Richard I. Masel, Amin Salehi-Khojin, Robert Kutz, ''[https://www.google.com/patents/US9815021 Electrocatalytic process for carbon dioxide conversion]'', US Patent 981501</ref> A number of polymers were tested and the imidazolium functionalized styrene polymer shown in the figure on the right showed the best performance.<ref name=sus /><ref>{{cite journal | last1=Kutz | first1=Robert B. | last2=Chen | first2=Qingmei | last3=Yang | first3=Hongzhou | last4=Sajjad | first4=Syed D. | last5=Liu | first5=Zengcai | last6=Masel | first6=I. Richard | title=Sustainion Imidazolium-Functionalized Polymers for Carbon Dioxide Electrolysis | journal=Energy Technology | date=2017 | volume=5 | issue=6 | pages=929–936 | doi=10.1002/ente.201600636 }}</ref> The membranes were trade named Sustainion. The use of Sustainion membranes raised the current and lifetime of the CO₂ electrolyzer into the commercially useful range.<ref name=sc2>{{cite journal | last1=Service | first1=Robert F. | title=Two new ways to turn 'garbage' carbon dioxide into fuel | journal=Science | date=2017 | doi=10.1126/science.aap8497 |doi-access=free}}</ref><ref name=SR>Steven K Ritter, "[https://cen.acs.org/articles/93/i13/CO2-Electrolyzer-Nears-Commercialization.html CO₂ Electrolyzer Nears Commercialization]", ''C&E News'', Volume 93 Issue 13 p. 30 . March 30, 2015</ref><ref name=gd>Mark Harris, "[https://www.theguardian.com/sustainable-business/2017/sep/14/entrepreneurs-turn-carbon-dioxide-into-fuels-artificial-photosynthesis The entrepreneurs turning carbon dioxide into fuels]", ''The Guardian'', 14 Sept 2017</ref><ref name=NS>"[https://www.nst.com.my/lifestyle/sunday-vibes/2017/12/310154/savvy-turning-carbon-dioxide-products SAVVY: Turning Carbon Dioxide into products]" ''New Straits Times'', Dec 3, 2017.</ref><ref name=WI2>Michael Foertsch, "[https://www.wired.de/collection/science/wissenschaft-co2-energie These methods turn CO2 into cheap energy]", ''Wired'', Sept 24, 2017</ref> Sustainion membranes have shown conductivities above 100 mS/cm under alkaline conditions at 60&nbsp;°C,<ref name=AW /> stability for thousands of hours in 1M KOH,<ref name=AW /> 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.<ref>{{cite journal | last1=Sajjad | first1=Syed D. | last2=Gao | first2=Yan | last3=Liu | first3=Zengcai | last4=Yang | first4=Hongzhou | last5=Masel | first5=Rich | title=Tunable-High Performance Sustainion™ Anion Exchange Membranes for Electrochemical Applications | journal=ECS Transactions | date=2017 | volume=77 | issue=11 | pages=1653–1656 | doi=10.1149/07711.1653ecst | bibcode=2017ECSTr..77k1653S }}</ref><ref name=AW /> 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.<ref>{{cite journal | last1=Liu | first1=Zengcai | last2=Yang | first2=Hongzhou | last3=Kutz | first3=Robert | last4=Masel | first4=Richard I. | title=CO₂Electrolysis to CO and O₂at High Selectivity, Stability and Efficiency Using Sustainion Membranes | journal=Journal of the Electrochemical Society | date=2018 | volume=165 | issue=15 | pages=J3371–J3377 | doi=10.1149/2.0501815jes }}</ref>

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Category:Electrochemical engineering Category:Chemical companies of the United States Category:Companies based in Boca Raton, Florida Category:Carbon dioxide Category:Climate change