Poly-tetrakis-5,10,15,20-(4-aminophenyl)porphyrin Films as Two-Electron Oxygen Reduction Photoelectrocatalysts for the Production of H2O2

Thin films of electropolymerized porphyrin polymers, poly-tetrakis-5,10,15,20-(4-aminophenyl)porphyrin (pTAPP) and its cobalt derivative (pCoTAPP), were found to be electrocatalysts and photoelectrocatalysts for the photosynthesis of hydrogen peroxide via a two-electron reduction of oxygen. On glassy carbon (GC) electrodes, oxygen reduction potentials were measured at −0.58 (GC), −0.40 (pTAPP), and −0.05 V (pCoTAPP), compared to Pt at +0.34 V (all vs Ag/AgCl). Thin electrode films were tested as photosynthetic electrocatalysts using small positive bias potentials (0.0 to +0.3 V) and specifically measuring H2O2 production. pTAPP achieved turnover numbers (TON) of 5–6, while pCoTAPP showed TON of 14–23. Faradaic efficiency in both cases was initially high, about 50%, but decreased over 1 h.

[1]  James R. McKone,et al.  Solar water splitting cells. , 2010, Chemical reviews.

[2]  S. Fukuzumi,et al.  Production of hydrogen peroxide as a sustainable solar fuel from water and dioxygen , 2013 .

[3]  R. Murray,et al.  Electrochemistry of various substituted aminophenyl iron porphyrins: Part I. Redox properties of dissolved, adsorbed and electropolymerized species , 1989 .

[4]  Paul Denholm,et al.  Role of Energy Storage with Renewable Electricity Generation (Report Summary) (Presentation) , 2010 .

[5]  P. Yang,et al.  Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water , 2015, Science.

[6]  A. Bettelheim,et al.  Dioxygen reduction and hydrogen peroxide dismutation using electropolymerized bilayers of cobalt + manganese tetrakis(o-aminophenyl)porphyrins , 1990 .

[7]  F. Du,et al.  Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction , 2009, Science.

[8]  A. Heller,et al.  Palladium catalysis of O2 reduction by electrons accumulated on TiO2 particles during photoassisted oxidation of organic compounds , 1992 .

[9]  Thomas J. Schmidt,et al.  Electrocatalysis for Polymer Electrolyte Fuel Cells: Recent Achievements and Future Challenges , 2012 .

[10]  B. A. White,et al.  Electrocatalysis of dioxygen reduction in aqueous acid and base by multimolecular layer films of electropolymerized cobalt tetra(o-aminophenyl)porphyrin , 1987 .

[11]  A. Bettelheim,et al.  Electrochemistry of various substituted aminophenyl iron porphyrins: Part II. catalytic reduction of dioxygen by electropolymerized films , 1989 .

[12]  K. Karlin,et al.  Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell. , 2012, Electrochimica acta.

[13]  G. Moore,et al.  Metalloporphyrin-modified semiconductors for solar fuel production , 2016, Chemical science.

[14]  C. Kubiak,et al.  Fe-Porphyrin-Based Metal–Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2 , 2015 .

[15]  J. Brédas,et al.  Polarons, bipolarons, and solitons in conducting polymers , 1985 .

[16]  Amir Kaplan,et al.  Electrocatalytic Activity towards Oxygen Reduction of Electropolymerized Cobalt Porphyrin Doped with Ionic-Liquid-Functionalized Graphene , 2015 .

[17]  J. Bisquert,et al.  Capacitance, spectroelectrochemistry and conductivity of polarons and bipolarons in a polydicarbazole based conducting polymer , 2008 .

[18]  G. Moore,et al.  Electrocatalytic and Optical Properties of Cobaloxime Catalysts Immobilized at a Surface-Grafted Polymer Interface , 2016 .

[19]  J. Cook,et al.  Reply to Comment on ‘Quantifying the consensus on anthropogenic global warming in the scientific literature’ , 2013 .

[20]  Qin Wu,et al.  Polarons, bipolarons, and side-by-side polarons in reduction of oligofluorenes. , 2012, Journal of the American Chemical Society.

[21]  S. Fukuzumi,et al.  Hydrogen Peroxide used as a Solar Fuel in One‐Compartment Fuel Cells , 2016 .

[22]  J. Baek,et al.  Metal-free catalysts for oxygen reduction reaction. , 2015, Chemical reviews.

[23]  Yusuke Yamada,et al.  Seawater usable for production and consumption of hydrogen peroxide as a solar fuel , 2016, Nature Communications.

[24]  S. Dutta.  A review on production, storage of hydrogen and its utilization as an energy resource , 2014 .

[25]  Kinetics of the reaction of hydrogen peroxide with some oxotitanium(IV) complexes as studied by a high-pressure stopped-flow technique , 1983 .

[26]  C. Wamser,et al.  Preparations and Electrochemical Characterizations of Conductive Porphyrin Polymers , 2015 .

[27]  Frank E. Osterloh,et al.  Photocatalysis versus Photosynthesis: A Sensitivity Analysis of Devices for Solar Energy Conversion and Chemical Transformations , 2017 .

[28]  C. Wamser,et al.  Synthesis and Characterization of Electropolymerized Nanostructured Aminophenylporphyrin Films , 2010 .

[29]  Chiyo Matsubara,et al.  Oxo[5, 10, 15, 20-tetra(4-pyridyl)porphyrinato]titanium(IV): an ultra-high sensitivity spectrophotometric reagent for hydrogen peroxide , 1992 .

[30]  B. A. White,et al.  Electrochemical polymerization of amino-, pyrrole-, and hydroxy-substituted tetraphenylporphyrins , 1987 .

[31]  C. C. Epley,et al.  Solvothermal preparation of an electrocatalytic metalloporphyrin MOF thin film and its redox hopping charge-transfer mechanism. , 2014, Journal of the American Chemical Society.