title: Direct electrolytic dissolution of silicate minerals for air CO2 mitigation and carbon-negative H2 production.
abstract: We experimentally demonstrate the direct coupling of silicate mineral dissolution with saline water electrolysis and H2 production to effect significant air CO2 absorption, chemical conversion, and storage in solution. In particular, we observed as much as a 10(5)-fold increase in OH(-) concentration (pH increase of up to 5.3 units) relative to experimental controls following the electrolysis of 0.25 M Na2SO4 solutions when the anode was encased in powdered silicate mineral, either wollastonite or an ultramafic mineral. After electrolysis, full equilibration of the alkalized solution with air led to a significant pH reduction and as much as a 45-fold increase in dissolved inorganic carbon concentration. This demonstrated significant spontaneous air CO2 capture, chemical conversion, and storage as a bicarbonate, predominantly as NaHCO3. The excess OH(-) initially formed in these experiments apparently resulted via neutralization of the anolyte acid, H2SO4, by reaction with the base mineral silicate at the anode, producing mineral sulfate and silica. This allowed the NaOH, normally generated at the cathode, to go unneutralized and to accumulate in the bulk electrolyte, ultimately reacting with atmospheric CO2 to form dissolved bicarbonate. Using nongrid or nonpeak renewable electricity, optimized systems at large scale might allow relatively high-capacity, energy-efficient (<300 kJ/mol of CO2 captured), and inexpensive (<$100 per tonne of CO2 mitigated) removal of excess air CO2 with production of carbon-negative H2. Furthermore, when added to the ocean, the produced hydroxide and/or (bi)carbonate could be useful in reducing sea-to-air CO2 emissions and in neutralizing or offsetting the effects of ongoing ocean acidification.
authors.affiliation: Institute of Marine Sciences, University of California, Santa Cruz, CA 95064, USA. rau4@llnl.gov
authors.forename: Greg H
authors.initials: GH
authors.lastname: Rau
authors.forename: Susan A
authors.initials: SA
authors.lastname: Carroll
authors.forename: William L
authors.initials: WL
authors.lastname: Bourcier
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Singleton
authors.forename: Megan M
authors.initials: MM
authors.lastname: Smith
authors.forename: Roger D
authors.initials: RD
authors.lastname: Aines
mesh_terms: D000143:Acids / Q000737:chemistry; D001639:Bicarbonates / Q000737:chemistry; D017610:Calcium Compounds / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry*; D057965:Carbon Sequestration; D002713:Chlorine / Q000737:chemistry; D004572:Electrolysis / Q000379:methods*; D004573:Electrolytes / Q000737:chemistry; D057232:Global Warming; D006859:Hydrogen / Q000737:chemistry*; D008903:Minerals / Q000737:chemistry; D009792:Oceans and Seas; D012623:Seawater / Q000737:chemistry; D017640:Silicates / Q000737:chemistry*; D012965:Sodium Chloride / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000143:Acids; D001639:Bicarbonates; D017610:Calcium Compounds; D004573:Electrolytes; D008903:Minerals; D017640:Silicates; D002245:Carbon Dioxide; D012965:Sodium Chloride; D002713:Chlorine; D006859:Hydrogen; C031293:calcium silicate
keywords: air capture; carbon dioxide; electrochemistry; hydrogen; mineral weathering