Direct propylene epoxidation via water activation over Pd-Pt electrocatalysts

Chung, Minju; Maalouf, Joseph H.; Adams, Jason S.; Jiang, Chenyu; Román-Leshkov, Yuriy; Manthiram, Karthish

doi:10.1126/science.adh4355

Title: Direct propylene epoxidation via water activation over Pd-Pt electrocatalysts

Journal Article · 03 January 2024 · Science

DOI: https://doi.org/10.1126/science.adh4355 · OSTI ID:2341589

^[1];

^[2];

^[3];

^[2];

^[3]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); California Institute of Technology
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)

Direct electrochemical propylene epoxidation by means of water-oxidation intermediates presents a sustainable alternative to existing routes that involve hazardous chlorine or peroxide reagents. Here, we report an oxidized palladium-platinum alloy catalyst (PdPtO_x/C), which reaches a Faradaic efficiency of 66 ± 5% toward propylene epoxidation at 50 milliamperes per square centimeter at ambient temperature and pressure. Embedding platinum into the palladium oxide crystal structure stabilized oxidized platinum species, resulting in improved catalyst performance. The reaction kinetics suggest that epoxidation on PdPtO_x/C proceeds through electrophilic attack by metal-bound peroxo intermediates. This work demonstrates an effective strategy for selective electrochemical oxygen-atom transfer from water, without mediators, for diverse oxygenation reactions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704; SC0023207

OSTI ID:: 2341589

Journal Information:: Science, Journal Name: Science Journal Issue: 6678 Vol. 383; ISSN 0036-8075

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Ullmann's Encyclopedia of Industrial Chemistry Ley, Claudia; Elvers, Barbara; Bellussi, Giuseppe https://doi.org/10.1002/14356007	reference-book	March 2000
Electrophilic Activation of Alkenes by Platinum(II): So Much More Than a Slow Version of Palladium(II) Chianese, Anthony R.; Lee, Stephen J.; Gagné, Michel R. Angewandte Chemie International Edition, Vol. 46, Issue 22 https://doi.org/10.1002/anie.200603954	journal	May 2007
Direct Epoxidation of Propylene over Stabilized Cu ⁺ Surface Sites on Titanium-Modified Cu ₂ O Yang, Xiaofang; Kattel, Shyam; Xiong, Ke Angewandte Chemie International Edition, Vol. 54, Issue 41 https://doi.org/10.1002/anie.201504538	journal	July 2015
Direct Oxygen Transfer from H₂O to Cyclooctene over Electron‐Rich RuO₂ Nanocrystals for Epoxidation and Hydrogen Evolution Lin, Xiu; Zhou, Zhaoyu; Li, Qi‐Yuan Angewandte Chemie International Edition, Vol. 61, Issue 35 https://doi.org/10.1002/anie.202207108	journal	July 2022
Electrophilicity index revisited Pal, Ranita; Chattaraj, Pratim Kumar Journal of Computational Chemistry, Vol. 44, Issue 3 https://doi.org/10.1002/jcc.26886	journal	May 2022
Electrocatalytic Synthesis of Propylene Oxide During Water Electrolysis Otsuka, K.; Ushiyama, T.; Yamanaka, I. Journal of Catalysis, Vol. 157, Issue 2 https://doi.org/10.1006/jcat.1995.1310	journal	December 1995
Anodic oxidation of propylene on a screen electrode Tse-Chuan, Chou; Jang-Chyang, Chang Chemical Engineering Science, Vol. 35, Issue 7 https://doi.org/10.1016/0009-2509(80)80051-0	journal	January 1980
Electrooxidation of olefins at a silver electrode Holbrook, L. Journal of Catalysis, Vol. 38, Issue 1-3 https://doi.org/10.1016/0021-9517(75)90090-1	journal	June 1975
Morphology and composition of Pt$z.sbnd;Pd alloy crystallites on SiO2 in reactive atmospheres*1 Chen, M. Journal of Catalysis, Vol. 56, Issue 2 https://doi.org/10.1016/0021-9517(79)90107-6	journal	February 1979
Kinetic and spectroscopic evidence for reaction pathways and intermediates for olefin epoxidation on Nb in *BEA Bregante, Daniel T.; Priyadarshini, Pranjali; Flaherty, David W. Journal of Catalysis, Vol. 348 https://doi.org/10.1016/j.jcat.2017.02.008	journal	April 2017
Electro-oxidation of propylene by palladium functionalized titanium hollow fibre electrodes Jong, R. P. H.; Dubbelman, E.; Mul, G. Journal of Catalysis, Vol. 416 https://doi.org/10.1016/j.jcat.2022.10.007	journal	December 2022
Opportunities and Challenges in Electrolytic Propylene Epoxidation Li, Hao; Abraham, Christina Susan; Anand, Megha The Journal of Physical Chemistry Letters, Vol. 13, Issue 9 https://doi.org/10.1021/acs.jpclett.2c00257	journal	February 2022
Mechanism of Chlorine-Mediated Electrochemical Ethylene Oxidation in Saline Water Chung, Minju; Jin, Kyoungsuk; Zeng, Joy Shuang ACS Catalysis, Vol. 10, Issue 23 https://doi.org/10.1021/acscatal.0c02810	journal	November 2020
Sintering of Pt Nanoparticles via Volatile PtO ₂ : Simulation and Comparison with Experiments Plessow, Philipp N.; Abild-Pedersen, Frank ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01646	journal	September 2016
Kinetic study of the epoxidation of 1-octene with hydrogen peroxide catalyzed by platinum(II) complexes. Evidence of the involvement of two metal species in the oxygen-transfer step Zanardo, Andrea; Pinna, Francesco; Michelin, Rino A. Inorganic Chemistry, Vol. 27, Issue 11 https://doi.org/10.1021/ic00284a027	journal	June 1988
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C. Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja407115p	journal	October 2013
MCPBA Epoxidation of Alkenes: Reinvestigation of Correlation between Rate and Ionization Potential Kim, Cheal; Traylor, Teddy G.; Perrin, Charles L. Journal of the American Chemical Society, Vol. 120, Issue 37 https://doi.org/10.1021/ja981531e	journal	September 1998
Tuning Single-Atom Dopants on Manganese Oxide for Selective Electrocatalytic Cyclooctene Epoxidation Chung, Minju; Jin, Kyoungsuk; Zeng, Joy S. Journal of the American Chemical Society, Vol. 144, Issue 38 https://doi.org/10.1021/jacs.2c04711	journal	September 2022
Reaction Mechanism and Selectivity Tuning of Propene Oxidation at the Electrochemical Interface Liu, Xiao-Chen; Wang, Tao; Zhang, Zhi-Ming Journal of the American Chemical Society, Vol. 144, Issue 45 https://doi.org/10.1021/jacs.2c09105	journal	November 2022
Size-Dependent Electrocatalytic Reduction of CO ₂ over Pd Nanoparticles Gao, Dunfeng; Zhou, Hu; Wang, Jing Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/jacs.5b00046	journal	March 2015
Suppressing Ion Transfer Enables Versatile Measurements of Electrochemical Surface Area for Intrinsic Activity Comparisons Yoon, Youngmin; Yan, Bing; Surendranath, Yogesh Journal of the American Chemical Society, Vol. 140, Issue 7 https://doi.org/10.1021/jacs.7b10966	journal	February 2018
Epoxidation of Cyclooctene Using Water as the Oxygen Atom Source at Manganese Oxide Electrocatalysts Jin, Kyoungsuk; Maalouf, Joseph H.; Lazouski, Nikifar Journal of the American Chemical Society, Vol. 141, Issue 15 https://doi.org/10.1021/jacs.9b02345	journal	March 2019
Trapping of Mobile Pt Species by PdO Nanoparticles under Oxidizing Conditions Carrillo, Cristihan; Johns, Tyne R.; Xiong, Haifeng The Journal of Physical Chemistry Letters, Vol. 5, Issue 12 https://doi.org/10.1021/jz5009483	journal	May 2014
Electrophilicity and Nucleophilicity Index for Radicals De Vleeschouwer, Freija; Van Speybroeck, Veronique; Waroquier, Michel Organic Letters, Vol. 9, Issue 14 https://doi.org/10.1021/ol071038k	journal	July 2007
Facet-dependent electrooxidation of propylene into propylene oxide over Ag3PO4 crystals Ke, Jingwen; Zhao, Jiankang; Chi, Mingfang Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-28516-0	journal	February 2022
Templated encapsulation of platinum-based catalysts promotes high-temperature stability to 1,100 °C Aitbekova, Aisulu; Zhou, Chengshuang; Stone, Michael L. Nature Materials, Vol. 21, Issue 11 https://doi.org/10.1038/s41563-022-01376-1	journal	October 2022
Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation: propene on palladium Winiwarter, Anna; Silvioli, Luca; Scott, Soren B. Energy & Environmental Science, Vol. 12, Issue 3 https://doi.org/10.1039/C8EE03426E	journal	January 2019
Chemisorbed oxygen or surface oxides steer the selectivity in Pd electrocatalytic propene oxidation observed by operando Pd L-edge X-ray absorption spectroscopy Koroidov, Sergey; Winiwarter, Anna; Diaz-Morales, Oscar Catalysis Science & Technology, Vol. 11, Issue 10 https://doi.org/10.1039/D0CY02134B	journal	January 2021
Direct epoxidation of propylene with water at a PtO_x anode using a solid-polymer-electrolyte electrolysis cell Iguchi, Shoji; Kataoka, Masashi; Hoshino, Ryosuke Catalysis Science & Technology, Vol. 12, Issue 2 https://doi.org/10.1039/D1CY01888D	journal	January 2022
Palladium oxidation leads to methane combustion activity: Effects of particle size and alloying with platinum Goodman, Emmett D.; Ye, Angela A.; Aitbekova, Aisulu The Journal of Chemical Physics, Vol. 151, Issue 15 https://doi.org/10.1063/1.5126219	journal	October 2019
Direct Oxidation of Propylene to Propylene Oxide with Molecular Oxygen: A Review Khatib, Sheima J.; Oyama, S. T. Catalysis Reviews, Vol. 57, Issue 3 https://doi.org/10.1080/01614940.2015.1041849	journal	June 2015
Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects Lei, Y.; Mehmood, F.; Lee, S. Science, Vol. 328, Issue 5975, p. 224-228 https://doi.org/10.1126/science.1185200	journal	April 2010
Chloride-mediated selective electrosynthesis of ethylene and propylene oxides at high current density Leow, Wan Ru; Lum, Yanwei; Ozden, Adnan Science, Vol. 368, Issue 6496 https://doi.org/10.1126/science.aaz8459	journal	June 2020
Ciliopathy patient variants reveal organelle-specific functions for TUBB4B in axonemal microtubules Dodd, Daniel O.; Mechaussier, Sabrina; Yeyati, Patricia L. Science, Vol. 384, Issue 6694 https://doi.org/10.1126/science.adf5489	journal	April 2024
De Haas–van Alphen spectroscopy and magnetic breakdown in moiré graphene Bocarsly, Matan; Uzan, Matan; Roy, Indranil Science, Vol. 383, Issue 6678 https://doi.org/10.1126/science.adh3499	journal	January 2024
Sequence basis of transcription initiation in the human genome Dudnyk, Kseniia; Cai, Donghong; Shi, Chenlai Science, Vol. 384, Issue 6694 https://doi.org/10.1126/science.adj0116	journal	April 2024
Genomic factors shape carbon and nitrogen metabolic niche breadth across Saccharomycotina yeasts Opulente, Dana A.; LaBella, Abigail Leavitt; Harrison, Marie-Claire Science, Vol. 384, Issue 6694 https://doi.org/10.1126/science.adj4503	journal	April 2024
Balancing risk-return decisions by manipulating the mesofrontal circuits in primates Sasaki, Ryo; Ohta, Yasumi; Onoe, Hirotaka Science, Vol. 383, Issue 6678 https://doi.org/10.1126/science.adj6645	journal	January 2024
Electrolytic Synthesis of Propene Oxide from Propene and Water in the Gas Phase Yamanaka, Ichiro Electrochemical and Solid-State Letters, Vol. 2, Issue 3 https://doi.org/10.1149/1.1390758	journal	January 1999
Alfred P. Sloan Foundation https://doi.org/10.13039/100000879	other	July 2009
Accounting for species’ thermodynamic activities changes mechanistic interpretations of electrochemical kinetic data WIlliams, Kindle; Limaye, Aditya; Weiss, Trent https://doi.org/10.26434/chemrxiv-2022-vk5z9	preprint	February 2022
Mechanistic Aspects of Vanadium-Catalysed Oxygen Transfer Reactions. Sams, Christian Klarner; Jørgensen, Karl Anker; Lindeman, Sergey V. Acta Chemica Scandinavica, Vol. 49 https://doi.org/10.3891/acta.chem.scand.49-0839	journal	January 1995
Data from: Direct propylene epoxidation via water activation over Pd-Pt electrocatalysts Chung, Minju; Maalouf, Joseph H.; Adams, Jason S. Dryad https://doi.org/10.5061/dryad.s7h44j1dd	dataset	January 2023

Similar Records

Crossing the Oxo‐Peroxo Wall for Selective Electrochemical Epoxidation

Journal Article · 2025 · Advanced Science · OSTI ID:2999871

Basera, Pooja; Mandal, Shyama Charan; Abild‐Pedersen, Frank; +1 more

Integrated process and dual-function catalyst for olefin epoxidation

Patent · 2002 · OSTI ID:875114

Zhou, Bing; Rueter, Michael

Epoxidation of propylene dimers and isomerization of mixtures obtained

Journal Article · 1988 · J. Appl. Chem. USSR (Engl. Transl.); (United States) · OSTI ID:6180767

Dobrev, D M; Kurtev, K S

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Direct propylene epoxidation via water activation over Pd-Pt electrocatalysts

Citation Formats

References (43)

Similar Records

Related Subjects