Design, Synthesis, and Evaluation of Noble Metal Nanoparticles and In Situ-Decorated Carbon-Supported Nanoparticle Electrocatalysts Using Hypergolic Reactions

Chalmpes, Nikolaos; Tantis, Iosif; Alsmaeil, Ahmed Wasel; Bourlinos, Athanasios B.; Giannelis, Emmanuel P.

doi:10.1021/acs.chemmater.4c02091

Design, Synthesis, and Evaluation of Noble Metal Nanoparticles and In Situ-Decorated Carbon-Supported Nanoparticle Electrocatalysts Using Hypergolic Reactions

Journal Article · Sat Oct 19 00:00:00 EDT 2024 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.4c02091· OSTI ID:3011350

^[1]; Tantis, Iosif ^[1]; Alsmaeil, Ahmed Wasel ^[1]; Bourlinos, Athanasios B. ^[2]; Giannelis, Emmanuel P. ^[1]

Cornell Univ., Ithaca, NY (United States)
Univ. of Ioannina (Greece)

Here, we report the first synthesis of metal nanoparticles and supported metal nanoparticles on carbon by using hypergolic reactions. Specifically, we report the synthesis of noble metal nanoparticles (Pt, Ag, and Au) using sodium hydride (NaH) as both an ignition trigger and a reducing agent for the corresponding metal salt precursors. In addition, we report the one-step, in situ synthesis of Pt nanoparticles supported on carbon by adding sucrose as the carbon source. The hypergolically synthesized nanoparticles display elliptical morphology and are more crystalline compared with those conventionally synthesized in solution using sodium borohydride (NaBH₄). When tested as electrocatalysts, the hypergolic Pt nanoparticles exhibit more than 2 times higher specific electrochemical active surface area (ECSA) and a higher half-wave potential (E_1/2) of 0.94 V vs the reversible hydrogen electrode (RHE) compared to the conventionally synthesized ones. In addition, the electrocatalyst based on the in situ synthesized carbon that was decorated with the Pt nanoparticles synthesized hypergolically outperforms an analogous, state of the art, commercial PtC system. For example, the former shows an attractive E_1/2 (0.94 V) compared with 0.9 V for the commercial PtC. Accelerated durability tests (ADT) in an alkaline environment add another advantage. After 10 000 cycles, the hypergolically synthesized system shows a smaller reduction of E_1/2 and less degradation compared to the commercial PtC (10 mV compared to ∼30 mV). The work described here represents the first reported synthesis using hypergolic reactions of metal nanoparticles as well as supported metal nanoparticles. The properties of the resulting electrocatalysts demonstrate the versatility and promise of the new approach in materials synthesis and open new avenues for further investigation as electrocatalysts.

View Accepted Manuscript (DOE)

Research Organization:: Cornell Univ., Ithaca, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019445

OSTI ID:: 3011350

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 21 Vol. 36; ISSN 1520-5002; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (60)

Noble Metal Nanomaterials for NIR‐Triggered Photothermal Therapy in Cancer Lv, Zhuoqian; He, Sijia; Wang, Youfu Advanced Healthcare Materials, Vol. 10, Issue 6 https://doi.org/10.1002/adhm.202001806	journal	January 2021
Noble Metal‐Based Multimetallic Nanoparticles for Electrocatalytic Applications Kim, Hyunjoong; Yoo, Tae Yong; Bootharaju, Megalamane S. Advanced Science, Vol. 9, Issue 1 https://doi.org/10.1002/advs.202104054	journal	November 2021
Porous Iron‐Nitrogen‐Carbon Electrocatalysts for Anion Exchange Membrane Fuel Cells (AEMFC) Ricciardi, Beatrice; Mecheri, Barbara; da Silva Freitas, Williane ChemElectroChem, Vol. 10, Issue 7 https://doi.org/10.1002/celc.202201115	journal	March 2023
Fitting A Square Peg into A Round Hole: Shape Control in Phase Transfer of Cubic Gold Nanoparticles Maack, Imke; Osmić, Milena; Mohrhusen, Lars ChemNanoMat, Vol. 7, Issue 6 https://doi.org/10.1002/cnma.202100080	journal	May 2021
The role of tannic acid and sodium citrate in the synthesis of silver nanoparticles Ranoszek-Soliwoda, Katarzyna; Tomaszewska, Emilia; Socha, Ewelina Journal of Nanoparticle Research, Vol. 19, Issue 8 https://doi.org/10.1007/s11051-017-3973-9	journal	August 2017
Simultaneous nucleation, condensation, and coagulation in aerosol reactors Pratsinis, Sotiris E. Journal of Colloid and Interface Science, Vol. 124, Issue 2 https://doi.org/10.1016/0021-9797(88)90180-4	journal	August 1988
Controlled synthesis of nanostructured particles by flame spray pyrolysis Mädler, L.; Kammler, H. K.; Mueller, R. Journal of Aerosol Science, Vol. 33, Issue 2 https://doi.org/10.1016/S0021-8502(01)00159-8	journal	February 2002
Key factors in chemical reduction by hydrazine for recovery of precious metals Chen, J. Paul; Lim, L. L. Chemosphere, Vol. 49, Issue 4 https://doi.org/10.1016/S0045-6535(02)00305-3	journal	October 2002
Effect of particle size on the activity and durability of the Pt/C electrocatalyst for proton exchange membrane fuel cells Xu, Zhuang; Zhang, Huamin; Zhong, Hexiang Applied Catalysis B: Environmental, Vol. 111-112 https://doi.org/10.1016/j.apcatb.2011.10.007	journal	January 2012
Bimetallic gold-platinum nanoparticles as a drug delivery system coated with a new drug to target glioblastoma Stavropoulou, Anastasia P.; Theodosiou, Maria; Sakellis, Elias Colloids and Surfaces B: Biointerfaces, Vol. 214 https://doi.org/10.1016/j.colsurfb.2022.112463	journal	June 2022
Improving cell performance for anion exchange membrane fuel cells with FeNC cathode by optimizing ionomer content Zhou, Yawen; Yu, Hongmei; Xie, Feng International Journal of Hydrogen Energy, Vol. 48, Issue 13 https://doi.org/10.1016/j.ijhydene.2022.11.057	journal	February 2023
Engineering carbon semi-tubes supported platinum catalyst for efficient oxygen reduction electrocatalysis Cai, Jialin; Chen, Junxiang; Chen, Yizhe iScience, Vol. 26, Issue 5 https://doi.org/10.1016/j.isci.2023.106730	journal	May 2023
Bi nanoparticles with different oxidation states embedded in porous carbon nanosheets as high-performance anode for lithium-ion battery Wang, Congli; Jiu, Hongfang; Song, Wei Journal of Alloys and Compounds, Vol. 960 https://doi.org/10.1016/j.jallcom.2023.170969	journal	October 2023
Research advances in unsupported Pt-based catalysts for electrochemical methanol oxidation Tian, Xin Long; Wang, Lijuan; Deng, Peilin Journal of Energy Chemistry, Vol. 26, Issue 6 https://doi.org/10.1016/j.jechem.2017.10.009	journal	November 2017
Empirical modeling of cathode electrode durability in polymer electrolyte fuel cells Messing, Marvin; Kjeang, Erik Journal of Power Sources, Vol. 451 https://doi.org/10.1016/j.jpowsour.2020.227750	journal	March 2020
Characterization of silver nanoparticles synthesized using Urtica dioica Linn. leaves and their synergistic effects with antibiotics Jyoti, Kumari; Baunthiyal, Mamta; Singh, Ajeet Journal of Radiation Research and Applied Sciences, Vol. 9, Issue 3 https://doi.org/10.1016/j.jrras.2015.10.002	journal	July 2016
Amino acid driven synthesis of gold nanoparticles: A comparative study on their biocompatibility Theodosiou, Maria; Chalmpes, Nikos; Gournis, Dimitrios Materials Chemistry and Physics, Vol. 319 https://doi.org/10.1016/j.matchemphys.2024.129260	journal	June 2024
Direct production of carbon nanosheets by self-ignition of pyrophoric lithium dialkylamides in air Baikousi, Maria; Chalmpes, Nikolaos; Spyrou, Konstantinos Materials Letters, Vol. 254 https://doi.org/10.1016/j.matlet.2019.07.019	journal	November 2019
Influence of a carbon support on the catalytic activity and durability of the Pt-based electrocatalysts Bayan, Yulia; Paperzh, Kirill; Pankov, Ilya Materials Letters, Vol. 368 https://doi.org/10.1016/j.matlet.2024.136670	journal	August 2024
Quantitative kinetic analysis on oxygen reduction reaction: A perspective Wang, Juan; Zhao, Chang-Xin; Liu, Jia-Ning Nano Materials Science, Vol. 3, Issue 3 https://doi.org/10.1016/j.nanoms.2021.03.006	journal	September 2021
Noble metal-based 1D and 2D electrocatalytic nanomaterials: Recent progress, challenges and perspectives Li, Yiju; Guo, Shaojun Nano Today, Vol. 28 https://doi.org/10.1016/j.nantod.2019.100774	journal	October 2019
Anion exchange polyelectrolytes for membranes and ionomers Chen, Nanjun; Lee, Young Moo Progress in Polymer Science, Vol. 113 https://doi.org/10.1016/j.progpolymsci.2020.101345	journal	February 2021
Experimental Methods for Quantifying the Activity of Platinum Electrocatalysts for the Oxygen Reduction Reaction Garsany, Yannick; Baturina, Olga A.; Swider-Lyons, Karen E. Analytical Chemistry, Vol. 82, Issue 15 https://doi.org/10.1021/ac100306c	journal	August 2010
Noble Metal Nanoparticle Biosensors: From Fundamental Studies toward Point-of-Care Diagnostics Geng, Hongya; Vilms Pedersen, Simon; Ma, Yun Accounts of Chemical Research, Vol. 55, Issue 5 https://doi.org/10.1021/acs.accounts.1c00598	journal	February 2022
Size Determination of Metal Nanoparticles Based on Electrochemically Measured Surface-Area-to-Volume Ratios Sharma, Jay N.; Pattadar, Dhruba K.; Mainali, Badri P. Analytical Chemistry, Vol. 90, Issue 15 https://doi.org/10.1021/acs.analchem.8b01905	journal	June 2018
Confined Ultrafine Pt in Porous Carbon Fibers and Their N-Enhanced Heavy d-π Effect Xiao, Yu-Xuan; Ying, Jie; Chen, Jiang-Bo Chemistry of Materials, Vol. 34, Issue 8 https://doi.org/10.1021/acs.chemmater.1c04400	journal	March 2022
“Surfactant-Free” Sodium Borohydride Nanoparticles with Enhanced Hydrogen Desorption Properties Wang, Ting; Aguey-Zinsou, Kondo-Francois ACS Applied Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1021/acsaem.0c01633	journal	September 2020
Synergetic Effect between Platinum Nanoparticles and Single Atoms Revealed in the Catalytic Mechanism of Traditional Pt/C for the Oxygen Reduction Reaction Dong, Yining; Li, He; Mei, Xuanhao ACS Applied Energy Materials, Vol. 7, Issue 13 https://doi.org/10.1021/acsaem.4c00073	journal	June 2024
Ambient Oxidation of Ultrasmall Platinum Nanoparticles on Microporous Carbon Catalyst Supports Banerjee, Ritubarna; Chen, Donna A.; Karakalos, Stavros ACS Applied Nano Materials, Vol. 1, Issue 10 https://doi.org/10.1021/acsanm.8b01548	journal	August 2018
Catalytic Advantages, Challenges, and Priorities in Alkaline Membrane Fuel Cells Firouzjaie, Horie Adabi; Mustain, William E. ACS Catalysis, Vol. 10, Issue 1 https://doi.org/10.1021/acscatal.9b03892	journal	November 2019
Unsupported Platinum-Based Electrocatalysts for Oxygen Reduction Reaction Tian, Xin Long; Xu, Yang Yang; Zhang, Wenyu ACS Energy Letters, Vol. 2, Issue 9 https://doi.org/10.1021/acsenergylett.7b00593	journal	August 2017
Self-Assembled Gold Nanoclusters for Bright Fluorescence Imaging and Enhanced Drug Delivery Yahia-Ammar, Akram; Sierra, Daniel; Mérola, Fabienne ACS Nano, Vol. 10, Issue 2 https://doi.org/10.1021/acsnano.5b07596	journal	January 2016
Antibacterial and Algicidal Effects of Porous Carbon Cuboid Nanoparticles Karageorgou, Dimitra; Thomou, Eleni; Vourvou, Nikolina T. ACS Omega, Vol. 4, Issue 3 https://doi.org/10.1021/acsomega.8b02018	journal	March 2019
Recent Advances in Noble Metal (Pt, Ru, and Ir)-Based Electrocatalysts for Efficient Hydrogen Evolution Reaction Li, Changqing; Baek, Jong-Beom ACS Omega, Vol. 5, Issue 1 https://doi.org/10.1021/acsomega.9b03550	journal	December 2019
Noble Metal Alloys for Plasmonics Gong, Chen; Leite, Marina S. ACS Photonics, Vol. 3, Issue 4 https://doi.org/10.1021/acsphotonics.5b00586	journal	February 2016
Noble Metals on the Nanoscale: Optical and Photothermal Properties and Some Applications in Imaging, Sensing, Biology, and Medicine Jain, Prashant K.; Huang, Xiaohua; El-Sayed, Ivan H. Accounts of Chemical Research, Vol. 41, Issue 12, p. 1578-1586 https://doi.org/10.1021/ar7002804	journal	December 2008
Different Sized Platinum Nanoparticles Supported on Carbon: An XPS Study on These Methanol Oxidation Catalysts Şen, Fatih; Gökaǧaç, Gülsün The Journal of Physical Chemistry C, Vol. 111, Issue 15 https://doi.org/10.1021/jp068381b	journal	March 2007
Size-dependent activity and selectivity of carbon dioxide photocatalytic reduction over platinum nanoparticles Dong, Chunyang; Lian, Cheng; Hu, Songchang Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03666-2	journal	March 2018
Ionomer distribution control in porous carbon-supported catalyst layers for high-power and low Pt-loaded proton exchange membrane fuel cells Ott, Sebastian; Orfanidi, Alin; Schmies, Henrike Nature Materials, Vol. 19, Issue 1 https://doi.org/10.1038/s41563-019-0487-0	journal	September 2019
Challenges in applying highly active Pt-based nanostructured catalysts for oxygen reduction reactions to fuel cell vehicles Kodama, Kensaku; Nagai, Tomoyuki; Kuwaki, Akira Nature Nanotechnology, Vol. 16, Issue 2 https://doi.org/10.1038/s41565-020-00824-w	journal	January 2021
Designing the next generation of proton-exchange membrane fuel cells Jiao, Kui; Xuan, Jin; Du, Qing Nature, Vol. 595, Issue 7867 https://doi.org/10.1038/s41586-021-03482-7	journal	July 2021
AuPt Alloy Nanostructures with Tunable Composition and Enzyme-like Activities for Colorimetric Detection of Bisulfide He, Weiwei; Han, Xiangna; Jia, Huimin Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/srep40103	journal	January 2017
Island-type growth of Au–Pt heterodimers: direct visualization of misfit dislocations and strain-relief mechanisms García-Negrete, C. A.; Knappett, B. R.; Schmidt, F. P. RSC Advances, Vol. 5, Issue 68 https://doi.org/10.1039/C5RA09808D	journal	January 2015
The impact of the morphology of the carbon support on the activity and stability of nanoparticle fuel cell catalysts Tuaev, Xenia; Rudi, Stefan; Strasser, Peter Catalysis Science & Technology, Vol. 6, Issue 23 https://doi.org/10.1039/C6CY01679K	journal	January 2016
The critical importance of ionomers on the electrochemical activity of platinum and platinum-free catalysts for anion-exchange membrane fuel cells Santori, Pietro G.; Mondal, Abhishek N.; Dekel, Dario R. Sustainable Energy & Fuels, Vol. 4, Issue 7 https://doi.org/10.1039/D0SE00483A	journal	January 2020
Challenges and opportunities in the bottom-up mechanochemical synthesis of noble metal nanoparticles de Oliveira, Paulo F. M.; Torresi, Roberto M.; Emmerling, Franziska Journal of Materials Chemistry A, Vol. 8, Issue 32 https://doi.org/10.1039/D0TA05183G	journal	January 2020
First synthesis of 2D materials by hypergolic reactions and evaluation of their dispersions for ink formulation: hexagonal boron nitride and fluorinated carbon nanosheets Chalmpes, Nikolaos; Bourlinos, Athanasios B.; Alsmaeil, Ahmed Wasel Materials Research Express, Vol. 11, Issue 3 https://doi.org/10.1088/2053-1591/ad2d42	journal	March 2024
Improved Accelerated Stress Tests for ORR Catalysts Using a Rotating Disk Electrode Nagai, Tomoyuki; Jahn, Christine; Jia, Hongfei Journal of The Electrochemical Society, Vol. 166, Issue 7 https://doi.org/10.1149/2.0161907jes	journal	January 2019
Accelerated Stress Testing by Rotating Disk Electrode for Carbon Corrosion in Fuel Cell Catalyst Supports Riese, Adam; Banham, Dustin; Ye, Siyu Journal of The Electrochemical Society, Vol. 162, Issue 7 https://doi.org/10.1149/2.0911507jes	journal	January 2015
Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media Ramaswamy, Nagappan; Mukerjee, Sanjeev Advances in Physical Chemistry, Vol. 2012 https://doi.org/10.1155/2012/491604	journal	March 2012
Current Strategies for Noble Metal Nanoparticle Synthesis Habibullah, Giyaullah; Viktorova, Jitka; Ruml, Tomas Nanoscale Research Letters, Vol. 16, Issue 1 https://doi.org/10.1186/s11671-021-03480-8	journal	March 2021
Hypergolic Materials Synthesis: A Review B. Bourlinos, Athanasios; Chalmpes, Nikolaos; Gournis, Dimitrios Journal of Nanotechnology Research, Vol. 04, Issue 02 https://doi.org/10.26502/jnr.2688-85210031	journal	January 2022
Hypergolic Materials Synthesis through Reaction of Fuming Nitric Acid with Certain Cyclopentadienyl Compounds Chalmpes, Nikolaos; Bourlinos, Athanasios B.; Šedajová, Veronika C, Vol. 6, Issue 4 https://doi.org/10.3390/c6040061	journal	October 2020
Platinum and Platinum Group Metal-Free Catalysts for Anion Exchange Membrane Fuel Cells Men Truong, Van; Richard Tolchard, Julian; Svendby, Jørgen Energies, Vol. 13, Issue 3 https://doi.org/10.3390/en13030582	journal	January 2020
Hypergolics in Carbon Nanomaterials Synthesis: New Paradigms and Perspectives Chalmpes, Nikolaos; Spyrou, Konstantinos; Vasilopoulos, Konstantinos C. Molecules, Vol. 25, Issue 9 https://doi.org/10.3390/molecules25092207	journal	May 2020
Carbon Nanostructures Derived through Hypergolic Reaction of Conductive Polymers with Fuming Nitric Acid at Ambient Conditions Chalmpes, Nikolaos; Moschovas, Dimitrios; Tantis, Iosif Molecules, Vol. 26, Issue 6 https://doi.org/10.3390/molecules26061595	journal	March 2021
Functional Carbon Materials Derived through Hypergolic Reactions at Ambient Conditions Chalmpes, Nikolaos; Asimakopoulos, Georgios; Spyrou, Konstantinos Nanomaterials, Vol. 10, Issue 3 https://doi.org/10.3390/nano10030566	journal	March 2020
Rapid Carbon Formation from Spontaneous Reaction of Ferrocene and Liquid Bromine at Ambient Conditions Chalmpes, Nikolaos; Tantis, Iosif; Bakandritsos, Aristides Nanomaterials, Vol. 10, Issue 8 https://doi.org/10.3390/nano10081564	journal	August 2020
Green Synthesis and Characterization of Silver Nanoparticles with High Antibacterial Activity Using Cell Extracts of Cyanobacterium Pseudanabaena/Limnothrix sp. Karageorgou, Dimitra; Zygouri, Panagiota; Tsakiridis, Theofylaktos Nanomaterials, Vol. 12, Issue 13 https://doi.org/10.3390/nano12132296	journal	July 2022
Noble Metals Functionalized on Graphene Oxide Obtained by Different Methods—New Catalytic Materials Iordache, Mihaela; Oubraham, Anisoara; Sorlei, Ioan-Sorin Nanomaterials, Vol. 13, Issue 4 https://doi.org/10.3390/nano13040783	journal	February 2023

Similar Records

Pt alloy nanoparticles decorated on large-size nitrogen-doped graphene tubes for highly stable oxygen-reduction catalysts

Journal Article · Sun Sep 02 20:00:00 EDT 2018 · Nanoscale · OSTI ID:1476277

Noncovalently functionalized graphitic mesoporous carbon as a stable support of Pt nanoparticles for oxygen reduction

Journal Article · Thu Dec 31 23:00:00 EST 2009 · Journal of Power Sources, 195(7 SP ISS):1805-1811 · OSTI ID:972939

Deposition of Platinum Nanoparticles on Carbon Nanotubes by Supercritical Fluid Method

Journal Article · Fri Nov 04 23:00:00 EST 2005 · Journal of Nanoscience and Nanotechnology, 5(11):1852-1857 · OSTI ID:15020484

Design, Synthesis, and Evaluation of Noble Metal Nanoparticles and In Situ-Decorated Carbon-Supported Nanoparticle Electrocatalysts Using Hypergolic Reactions

Citation Formats

References (60)

Similar Records

Related Subjects