Laser-Induced Pd-PdO/rGO Catalysts for Enhanced Electrocatalytic Conversion of Nitrate into Ammonia

Overview

Journal ACS Appl Mater Interfaces

Publisher American Chemical Society

Specialties Biomedical Engineering
Biotechnology

Date 2024 Jul 4

PMID 38961637

Authors

James Ebenezer

Aneena Lal

Parthiban Velayudham

Arie Borenstein

Alex Schechter

Affiliations

Soon will be listed here.

Abstract

Electrochemical reduction of nitrate to ammonia (eNORR) is proposed as a sustainable solution for high-rate ammonia synthesis under ambient conditions. The complex, multistep eNORR mechanism necessitates the use of a catalyst for the complete conversion of nitrate to ammonia. Our research focuses on developing a novel Pd-PdO doped in a reduced graphene oxide (rGO) composite catalyst synthesized via a laser-assisted one-step technique. This catalyst demonstrates dual functionality: palladium (Pd) boosts hydrogen adsorption, while its oxide (PdO) demonstrates considerable nitrogen adsorption affinity and exhibits a maximum ammonia yield of 5456.4 ± 453.4 μg/h/cm at -0.6 V vs reversible hydrogen electrode (RHE), with significant yields for nitrite and hydroxylamine under ambient conditions in a nitrate-containing alkaline electrolyte. At a lower potential of -0.1 V, the catalyst exhibited a minimal hydrogen evolution reaction of 3.1 ± 2.2% while achieving high ammonia selectivity (74.9 ± 4.4%), with the balance for nitrite and hydroxylamine. Additionally, the catalyst's stability and activity can be regenerated through the electrooxidation of Pd.

References

Chen A, Ostrom C . Palladium-Based Nanomaterials: Synthesis and Electrochemical Applications. Chem Rev. 2015; 115(21):11999-2044. DOI: 10.1021/acs.chemrev.5b00324. View

Fan A, Steinberg V . Health implications of nitrate and nitrite in drinking water: an update on methemoglobinemia occurrence and reproductive and developmental toxicity. Regul Toxicol Pharmacol. 1996; 23(1 Pt 1):35-43. DOI: 10.1006/rtph.1996.0006. View

Lee H, Kim J, Lee K, Park K, Bae J, Mubarak M . Elucidation of an intrinsic parameter for evaluating the electrical quality of graphene flakes. Sci Rep. 2019; 9(1):557. PMC: 6346114. DOI: 10.1038/s41598-018-37010-x. View

Giovanni M, Poh H, Ambrosi A, Zhao G, Sofer Z, Sanek F . Noble metal (Pd, Ru, Rh, Pt, Au, Ag) doped graphene hybrids for electrocatalysis. Nanoscale. 2012; 4(16):5002-8. DOI: 10.1039/c2nr31077e. View

Han Y, Zhang X, Cai W, Zhao H, Zhang Y, Sun Y . Facet-controlled palladium nanocrystalline for enhanced nitrate reduction towards ammonia. J Colloid Interface Sci. 2021; 600:620-628. DOI: 10.1016/j.jcis.2021.05.061. View

Wang Y, Xu A, Wang Z, Huang L, Li J, Li F . Enhanced Nitrate-to-Ammonia Activity on Copper-Nickel Alloys via Tuning of Intermediate Adsorption. J Am Chem Soc. 2020; 142(12):5702-5708. DOI: 10.1021/jacs.9b13347. View

Yu W, Jiang H, Fang J, Song S . Designing an Electron-Deficient Pd/NiCoO Bifunctional Electrocatalyst with an Enhanced Hydrodechlorination Activity to Reduce the Consumption of Pd. Environ Sci Technol. 2021; 55(14):10087-10096. DOI: 10.1021/acs.est.1c01922. View

Brownson D, Kampouris D, Banks C . Graphene electrochemistry: fundamental concepts through to prominent applications. Chem Soc Rev. 2012; 41(21):6944-76. DOI: 10.1039/c2cs35105f. View

Shu J, Li R, Lian Z, Zhang W, Jin R, Yang H . In-situ oxidation of Palladium-Iridium nanoalloy anchored on Nitrogen-doped graphene as an efficient catalyst for methanol electrooxidation. J Colloid Interface Sci. 2021; 605:44-53. DOI: 10.1016/j.jcis.2021.07.056. View

10.

Dresselhaus M, Jorio A, Hofmann M, Dresselhaus G, Saito R . Perspectives on carbon nanotubes and graphene Raman spectroscopy. Nano Lett. 2010; 10(3):751-8. DOI: 10.1021/nl904286r. View

11.

Yao Y, Zhu S, Wang H, Li H, Shao M . A Spectroscopic Study of Electrochemical Nitrogen and Nitrate Reduction on Rhodium Surfaces. Angew Chem Int Ed Engl. 2020; 59(26):10479-10483. DOI: 10.1002/anie.202003071. View

12.

Wang Y, Shu S, Peng M, Hu L, Lv X, Shen Y . Dual-site electrocatalytic nitrate reduction to ammonia on oxygen vacancy-enriched and Pd-decorated MnO nanosheets. Nanoscale. 2021; 13(41):17504-17511. DOI: 10.1039/d1nr04962c. View

13.

Marcano D, Kosynkin D, Berlin J, Sinitskii A, Sun Z, Slesarev A . Improved synthesis of graphene oxide. ACS Nano. 2010; 4(8):4806-14. DOI: 10.1021/nn1006368. View

14.

Gao Z, Lai Y, Tao Y, Xiao L, Zhang L, Luo F . Constructing Well-Defined and Robust Th-MOF-Supported Single-Site Copper for Production and Storage of Ammonia from Electroreduction of Nitrate. ACS Cent Sci. 2021; 7(6):1066-1072. PMC: 8228586. DOI: 10.1021/acscentsci.1c00370. View

15.

Scalari G, Maissen C, Turcinkova D, Hagenmuller D, De Liberato S, Ciuti C . Ultrastrong coupling of the cyclotron transition of a 2D electron gas to a THz metamaterial. Science. 2012; 335(6074):1323-6. DOI: 10.1126/science.1216022. View

16.

Schurig D, Mock J, Justice B, Cummer S, Pendry J, Starr A . Metamaterial electromagnetic cloak at microwave frequencies. Science. 2006; 314(5801):977-80. DOI: 10.1126/science.1133628. View

17.

Liu Q, Xu W, Huang H, Shou H, Low J, Dai Y . Spectroscopic visualization of reversible hydrogen spillover between palladium and metal-organic frameworks toward catalytic semihydrogenation. Nat Commun. 2024; 15(1):2562. PMC: 10959988. DOI: 10.1038/s41467-024-46923-3. View