Direct H2O2 Synthesis, without H2 Gas.

We report here the direct hydrogenation of O2 gas to form hydrogen peroxide (H2O2) using a membrane reactor without H2 gas. Hydrogen is sourced from water, and the reactor is driven by electricity. Hydrogenation chemistry is achieved using a hydrogen-permeable Pd foil that separates an electrolysis chamber that generates reactive H atoms, from a hydrogenation chamber where H atoms react with O2 to form H2O2. Our results show that the concentration of H2O2 can be increased ∼8 times (from 56.5 to 443 mg/L) by optimizing the ratio of methanol-to-water in the chemical chamber, and through catalyst design. We demonstrate that the concentration of H2O2 is acutely sensitive to the H2O2 decomposition rate. This decomposition rate can be minimized by using AuPd alloy catalysts instead of pure Pd. This study presents a new pathway to directly synthesize H2O2 using water electrolysis without ever using H2 gas.

[1]  J. Maillard,et al.  A residue-free approach to water disinfection using catalytic in situ generation of reactive oxygen species , 2021, Nature Catalysis.

[2]  D. Dvorak,et al.  Physical Separation of H2 Activation from Hydrogenation Chemistry Reveals the Specific Role of Secondary Metal Catalysts. , 2021, Angewandte Chemie.

[3]  Zishuai Zhang,et al.  Electrolysis Can Be Used to Resolve Hydrogenation Pathways at Palladium Surfaces in a Membrane Reactor , 2021, JACS Au.

[4]  A. Karim,et al.  Solvent molecules form surface redox mediators in situ and cocatalyze O2 reduction on Pd , 2021, Science.

[5]  C. Berlinguette,et al.  Hydrogenation without H2 Using a Palladium Membrane Flow Cell , 2020 .

[6]  K. Domen,et al.  Minimizing energy demand and environmental impact for sustainable NH3 and H2O2 production—A perspective on contributions from thermal, electro-, and photo-catalysis , 2020, Applied Catalysis A: General.

[7]  T. A. Hatton,et al.  Electrosynthesis of Hydrogen Peroxide by Phase-Transfer Catalysis , 2019, Joule.

[8]  Yang Xia,et al.  Direct electrosynthesis of pure aqueous H2O2 solutions up to 20% by weight using a solid electrolyte , 2019, Science.

[9]  S. C. Perry,et al.  Electrochemical synthesis of hydrogen peroxide from water and oxygen , 2019, Nature Reviews Chemistry.

[10]  C. Berlinguette,et al.  Efficient Electrocatalytic Hydrogenation with a Palladium Membrane Reactor. , 2019, Journal of the American Chemical Society.

[11]  G. Hutchings,et al.  Recent Advances in the Direct Synthesis of H2O2 , 2018, ChemCatChem.

[12]  C. Berlinguette,et al.  Complete electron economy by pairing electrolysis with hydrogenation , 2018, Nature Catalysis.

[13]  C. Mullins,et al.  Surface Alloy Composition Controlled O2 Activation on Pd–Au Bimetallic Model Catalysts , 2018 .

[14]  Sebastian Kunz,et al.  Direct synthesis of H2O2 on Pd and AuxPd1 clusters: Understanding the effects of alloying Pd with Au , 2018 .

[15]  C. Berlinguette,et al.  Rapid Quantification of Film Thickness and Metal Loading for Electrocatalytic Metal Oxide Films , 2017 .

[16]  Hua Li,et al.  Green and efficient epoxidation of propylene with hydrogen peroxide (HPPO process) catalyzed by hollow TS-1 zeolite: A 1.0 kt/a pilot-scale study , 2016 .

[17]  G. Hutchings,et al.  Palladium-tin catalysts for the direct synthesis of H2O2 with high selectivity , 2016, Science.

[18]  N. Wilson,et al.  Mechanism for the Direct Synthesis of H2O2 on Pd Clusters: Heterolytic Reaction Pathways at the Liquid-Solid Interface. , 2016, Journal of the American Chemical Society.

[19]  J. García-Serna,et al.  Effect of low hydrogen to palladium molar ratios in the direct synthesis of H2O2 in water in a trickle bed reactor , 2015 .

[20]  K. Yoshizawa,et al.  Mechanistic aspects in the direct synthesis of hydrogen peroxide on PdAu catalyst from first principles , 2015 .

[21]  Hideki Yamamoto,et al.  Solubility of Oxygen in Organic Solvents and Calculation of the Hansen Solubility Parameters of Oxygen , 2014 .

[22]  Alberto E. Cassano,et al.  Chemical Disinfection with H2O2. The proposal of a Reaction Kinetic Model , 2012 .

[23]  T. Ishihara,et al.  Theoretical Revisit of the Direct Synthesis of H2O2 on Pd and Au@Pd Surfaces: A Comprehensive Mechanistic Study , 2011 .

[24]  Jonghee Han,et al.  On the Role of Pd Ensembles in Selective H2O2 Formation on PdAu Alloys , 2009 .

[25]  G. Hutchings,et al.  Switching Off Hydrogen Peroxide Hydrogenation in the Direct Synthesis Process , 2009, Science.

[26]  G. Hutchings,et al.  Palladium and gold-palladium catalysts for the direct synthesis of hydrogen peroxide. , 2008, Angewandte Chemie.

[27]  T. Ishihara,et al.  Theoretical Study of the Direct Synthesis of H2O2 on Pd and Pd/Au Surfaces , 2008 .

[28]  J. Fierro,et al.  Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. , 2006, Angewandte Chemie.

[29]  J. Lunsford,et al.  Controlling factors in the direct formation of H2O2 from H2 and O2 over a Pd/SiO2 catalyst in ethanol , 2006 .

[30]  R. Hage,et al.  Applications of transition-metal catalysts to textile and wood-pulp bleaching. , 2005, Angewandte Chemie.

[31]  J. Lunsford,et al.  A mechanistic study of H2O2 and H2O formation from H2 and O2 catalyzed by palladium in an aqueous medium , 2004 .

[32]  Takeshi Onizawa,et al.  Direct and continuous production of hydrogen peroxide with 93 % selectivity using a fuel-cell system. , 2003, Angewandte Chemie.

[33]  M. Enyo,et al.  HYDROGEN ABSORPTION BY PALLADIUM ELECTRODE POLARIZED IN SULFURIC ACID SOLUTION CONTAINING SURFACE ACTIVE SUBSTANCES. I. THE CATHODIC REGION , 1981 .

[34]  F. Scheffer,et al.  Untersuchungsmethoden der allgemeinen und anorganisch-chemischen Technologie und der Metallurgie , 1939 .