An investigation of the physical and chemical changes of Pd nanoparticles on carbon supports in response to the release of hydrogen from aqueous formate solutions

Byun, Mi Yeon; Le, Thuy D.; Strange, Nicholas A.; Park, Hyoju; Kovarik, Libor; Autrey, Tom; Bowden, Mark E.

doi:10.1016/j.ijhydene.2025.152890

Title: An investigation of the physical and chemical changes of Pd nanoparticles on carbon supports in response to the release of hydrogen from aqueous formate solutions

Journal Article · Fri Dec 05 00:00:00 UTC 2025 · International Journal of Hydrogen Energy

DOI: https://doi.org/10.1016/j.ijhydene.2025.152890 · OSTI ID:3010925

^[1];

^[1]; Strange, Nicholas A. ^[2];

^[1]; Kovarik, Libor ^[1];

^[1];

^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Palladium nanoparticles on carbon supports (Pd/C) are effective for catalyzing hydrogen release from aqueous formate solutions but typically suffer from a gradual decrease of activity. This study finds two primary factors influencing activity: (i) the number of available surface Pd sites, and (ii) metal-support interactions which depend on the nature of the C support. We propose that the Pd/C catalyst is structure insensitive and undergoes Ostwald ripening to yield an active ‘conditioned’ catalyst with dispersion plateauing between ca. 15–20 %. Contrary to earlier studies, in-situ XANES experiments show that PdO is not an active catalyst for formate dehydrogenation. Calcination of Pd/C before dehydrogenation increases the catalytic activity which suggests a beneficial, albeit temporary, modification of the metal support interaction. N-containing supports minimize nanoparticle growth and also increase activity through a metal-support interaction. In conclusion, these findings advance our understanding of catalyst evolution and stability in formate dehydrogenation systems.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO)

Grant/Contract Number:: AC05-76RL01830; AC36-08GO28308

OSTI ID:: 3010925

Report Number(s):: PNNL-SA--215117

Journal Information:: International Journal of Hydrogen Energy, Journal Name: International Journal of Hydrogen Energy Vol. 200; ISSN 0360-3199

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (32)

Dehydrogenation of Formic Acid at Room Temperature: Boosting Palladium Nanoparticle Efficiency by Coupling with Pyridinic-Nitrogen-Doped Carbon Bi, Qing-Yuan; Lin, Jian-Dong; Liu, Yong-Mei Angewandte Chemie International Edition, Vol. 55, Issue 39 https://doi.org/10.1002/anie.201605961	journal	August 2016
Highly Efficient Hydrogen Storage System Based on Ammonium Bicarbonate/Formate Redox Equilibrium over Palladium Nanocatalysts Su, Ji; Yang, Lisha; Lu, Mi ChemSusChem, Vol. 8, Issue 5 https://doi.org/10.1002/cssc.201403251	journal	February 2015
Palladium on Nitrogen-Doped Mesoporous Carbon: A Bifunctional Catalyst for Formate-Based, Carbon-Neutral Hydrogen Storage Wang, Fanan; Xu, Jinming; Shao, Xianzhao ChemSusChem, Vol. 9, Issue 3 https://doi.org/10.1002/cssc.201501376	journal	January 2016
Highly Stable Single-Atom Catalyst with Ionic Pd Active Sites Supported on N-Doped Carbon Nanotubes for Formic Acid Decomposition Podyacheva, Olga Y.; Bulushev, Dmitri A.; Suboch, Arina N. ChemSusChem, Vol. 11, Issue 21 https://doi.org/10.1002/cssc.201801679	journal	September 2018
Formate salts as chemical carriers in hydrogen storage and transportation Zaidman, B.; Wiener, H.; Sasson, Y. International Journal of Hydrogen Energy, Vol. 11, Issue 5 https://doi.org/10.1016/0360-3199(86)90154-0	journal	January 1986
Hydrogen storage by the bicarbonate/formate reaction. Studies on the activity of Pd catalysts Kramer, H. International Journal of Hydrogen Energy, Vol. 20, Issue 3 https://doi.org/10.1016/0360-3199(94)E0025-T	journal	March 1995
Novel nanoporous N-doped carbon-supported ultrasmall Pd nanoparticles: Efficient catalysts for hydrogen storage and release Koh, Katherine; Jeon, Mina; Chevrier, Daniel M. Applied Catalysis B: Environmental, Vol. 203 https://doi.org/10.1016/j.apcatb.2016.10.080	journal	April 2017
Understanding the effect of Pd size on formic acid dehydrogenation via size-controlled Pd/C catalysts prepared by NaBH4 treatment Kim, Yongwoo; Kim, Do Heui Applied Catalysis B: Environmental, Vol. 244 https://doi.org/10.1016/j.apcatb.2018.12.008	journal	May 2019
Efficient Pd on carbon catalyst for ammonium formate dehydrogenation: Effect of surface oxygen functional groups Dong, Zhun; Mukhtar, Ahmad; Ludwig, Thomas Applied Catalysis B: Environmental, Vol. 321 https://doi.org/10.1016/j.apcatb.2022.122015	journal	February 2023
Formic acid dehydrogenation attained by Pd nanoparticles-based catalysts supported on MWCNT-C3N4 composites Navlani-García, Miriam; Salinas-Torres, David; Vázquez-Álvarez, Francisco Daniel Catalysis Today, Vol. 397-399 https://doi.org/10.1016/j.cattod.2021.07.019	journal	August 2022
Electronically modified Pd catalysts supported on N-doped carbon for the dehydrogenation of formic acid Jeon, Mina; Han, Da Jung; Lee, Kug-Seung International Journal of Hydrogen Energy, Vol. 41, Issue 34 https://doi.org/10.1016/j.ijhydene.2016.04.102	journal	September 2016
Effect of precursor on the hydrogen evolution activity and recyclability of Pd-Supported graphitic carbon nitride Shirman, Ron; Bahuguna, Ashish; Sasson, Yoel International Journal of Hydrogen Energy, Vol. 46, Issue 73 https://doi.org/10.1016/j.ijhydene.2021.08.178	journal	October 2021
Effect of oxygen on formic acid decomposition over Pd catalyst Xu, Pengyu; Bernal-Juan, Fernando D.; Lefferts, Leon Journal of Catalysis, Vol. 394 https://doi.org/10.1016/j.jcat.2020.10.032	journal	February 2021
Ultrafine Pd nanoparticles on amine-functionalized carbon nanotubes for hydrogen production from formic acid Kim, Yongwoo; Lee, Hwangho; Yang, Seungdo Journal of Catalysis, Vol. 404 https://doi.org/10.1016/j.jcat.2021.10.007	journal	December 2021
Challenges and opportunities for using formate to store, transport, and use hydrogen Grubel, Katarzyna; Jeong, Hyangsoo; Yoon, Chang Won Journal of Energy Chemistry, Vol. 41 https://doi.org/10.1016/j.jechem.2019.05.016	journal	February 2020
A versatile machine learning workflow for high-throughput analysis of supported metal catalyst particles Genc, Arda; Marlowe, Justin; Jalil, Anika Ultramicroscopy, Vol. 271 https://doi.org/10.1016/j.ultramic.2025.114116	journal	May 2025
Pd–PdO Interface as Active Site for HCOOH Selective Dehydrogenation at Ambient Condition Lv, Qing; Meng, Qinglei; Liu, Weiwei The Journal of Physical Chemistry C, Vol. 122, Issue 4 https://doi.org/10.1021/acs.jpcc.7b08105	journal	January 2018
Fundamental Mechanisms of Reversible Dehydrogenation of Formate on N-Doped Graphene-Supported Pd Nanoparticles Shin, Dong Yun; Kim, Min-Su; Kwon, Jeong An The Journal of Physical Chemistry C, Vol. 123, Issue 3 https://doi.org/10.1021/acs.jpcc.8b07002	journal	December 2018
Influence of the Molecular Structure on the Electrocatalytic Hydrogenation of Carbonyl Groups and H₂ Evolution on Pd Meyer, Laura C.; Sanyal, Udishnu; Stoerzinger, Kelsey A. ACS Catalysis, Vol. 12, Issue 19 https://doi.org/10.1021/acscatal.2c03207	journal	September 2022
Diamine-Alkalized Reduced Graphene Oxide: Immobilization of Sub-2 nm Palladium Nanoparticles and Optimization of Catalytic Activity for Dehydrogenation of Formic Acid Song, Fu-Zhan; Zhu, Qi-Long; Tsumori, Nobuko ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01411	journal	August 2015
Tandem Nitrogen Functionalization of Porous Carbon: Toward Immobilizing Highly Active Palladium Nanoclusters for Dehydrogenation of Formic Acid Li, Zhangpeng; Yang, Xinchun; Tsumori, Nobuko ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.7b00053	journal	March 2017
Development of an Autothermal Formate-Based Hydrogen Generator: From Optimization of Formate Dehydrogenation Conditions to Thermal Integration with Fuel Cells Hwang, Yeon Jin; Kwon, Yearang; Kim, Yongmin ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 26 https://doi.org/10.1021/acssuschemeng.0c02775	journal	June 2020
Strategy for Efficient H₂ Production from a Mixture of Formic Acid and Formate using Operando pH Measurements Kim, Chan; Lee, Kimoon; Yoo, Il-Han ACS Sustainable Chemistry & Engineering, Vol. 10, Issue 2 https://doi.org/10.1021/acssuschemeng.1c06603	journal	January 2022
Achieving gigawatt-scale green hydrogen production and seasonal storage at industrial locations across the U.S Breunig, Hanna; Rosner, Fabian; Saqline, Syed Nature Communications, Vol. 15, Issue 1 https://doi.org/10.1038/s41467-024-53189-2	journal	October 2024
Automatic high-pressure hydrogen generation from formic acid in the presence of nano-Pd heterogeneous catalysts at mild temperatures Zhong, Heng; Iguchi, Masayuki; Song, Fu-Zhan Sustainable Energy & Fuels, Vol. 1, Issue 5 https://doi.org/10.1039/C7SE00131B	journal	January 2017
Anchoring of palladium nanoparticles on N-doped mesoporous carbon Warczinski, Lisa; Hu, Bin; Eckhard, Till Physical Chemistry Chemical Physics, Vol. 22, Issue 37 https://doi.org/10.1039/D0CP03234D	journal	January 2020
Size-dependent hydrogen trapping in palladium nanoparticles Liu, Wang; Magnin, Yann; Förster, Daniel Journal of Materials Chemistry A, Vol. 9, Issue 16 https://doi.org/10.1039/D0TA12174F	journal	January 2021
Green steel: design and cost analysis of hydrogen-based direct iron reduction Rosner, Fabian; Papadias, Dionissios; Brooks, Kriston Energy & Environmental Science, Vol. 16, Issue 10 https://doi.org/10.1039/D3EE01077E	journal	January 2023
Using earth abundant materials for long duration energy storage: electro-chemical and thermo-chemical cycling of bicarbonate/formate Gutiérrez, Oliver Y.; Grubel, Katarzyna; Kothandaraman, Jotheeswari Green Chemistry, Vol. 25, Issue 11 https://doi.org/10.1039/D3GC00219E	journal	January 2023
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Research Requirements to Move the Bar forward Using Aqueous Formate Salts as H2 Carriers for Energy Storage Applications Grubel, Katarzyna; Su, Ji Journal of Energy and Power Technology, Vol. 2, Issue 4 https://doi.org/10.21926/jept.2004016	journal	November 2020
Application of Liquid Hydrogen Carriers in Hydrogen Steelmaking Andersson, Joakim Energies, Vol. 14, Issue 5 https://doi.org/10.3390/en14051392	journal	March 2021

Similar Records

Silver-decorated palladium on carbon catalyst for enhanced ammonium formate dehydrogenation

Journal Article · Fri Dec 08 00:00:00 UTC 2023 · Catalysis Science and Technology · OSTI ID:2283283

Dong, Zhun; Mukhtar, Ahmad; Ludwig, Thomas; +8 more

Efficient Pd on carbon catalyst for ammonium formate dehydrogenation: Effect of surface oxygen functional groups

Journal Article · Tue Sep 27 00:00:00 UTC 2022 · Applied Catalysis. B, Environmental · OSTI ID:1924492

Dong, Zhun; Mukhtar, Ahmad; Ludwig, Thomas K.; +7 more

Single-Atom Alloy Formation via Reaction-Driven Catalyst Restructuring

Journal Article · Mon Jul 22 00:00:00 UTC 2024 · Journal of the American Chemical Society · OSTI ID:2511381

Giannakakis, Georgios; Soni, Yogita; Novotny, Gregory L.; +7 more

Related Subjects

Formate dehydrogenation
Hydrogen Storage
Ostwald ripening; Metal-support interaction
Pd/C catalysts

Title: An investigation of the physical and chemical changes of Pd nanoparticles on carbon supports in response to the release of hydrogen from aqueous formate solutions

Citation Formats

References (32)

Similar Records

Related Subjects