Trimetallic Nanoalloy of NiFeCo Embedded in Phosphidated Nitrogen Doped Carbon Catalyst for Efficient Electro-Oxidation of Kraft Lignin

Polymers (Basel). 2022 Sep 9;14(18):3781. doi: 10.3390/polym14183781.

Abstract

Recently, electro-oxidation of kraft lignin has been reported as a prominent electrochemical reaction to generate hydrogen at lower overpotential in alkaline water electrolysis. However, this reaction is highly limited by the low performance of existing electrocatalysts. Herein, we report a novel yet effective catalyst that comprises nonprecious trimetallic (Ni, Fe, and Co) nanoalloy as a core in a phosphidated nitrogen-doped carbon shell (referred to as sample P-NiFeCo/NC) for efficient electro-oxidation of kraft lignin at different temperatures in alkaline medium. The as-synthesized catalyst electro-oxidizes lignin only at 0.2 V versus Hg/HgO, which is almost three times less positive potential than in the conventional oxygen evolution reaction (0.59 V versus Hg/HgO) at 6.4 mA/cm2 in 1 M KOH. The catalyst demonstrates a turnover frequency (TOF) three to five times greater in lignin containing 1 M KOH than that of pure 1 M KOH. More importantly, the catalyst P-NiFeCo/NC shows theoretical hydrogen production of about 0.37 μmoles/min in the presence of lignin, much higher than that in pure 1 M KOH (0.0078 μ moles/min). Thus, this work verifies the benefit of the NiFeCo nanoalloy incorporated in carbon matrix, providing the way to realize a highly active catalyst for the electro-oxidation of kraft lignin.

Keywords: doped carbon; hydrogen generation; lignin electro-oxidation; non noble metals; oxygen evolution reaction.

Grants and funding

This research was financially supported by the RCGI–Research Centre for Gas Innovation, hosted by the University of São Paulo (USP) and sponsored by FAPESP–São Paulo Research Foundation (#2020/15230-5) and Shell Brasil, and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas, and Biofuels Agency) through the R&D levy regulation. H.V. also acknowledges financial support of FAPESP (#2019/22183-6), and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) under grant #306060/2017-5. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior– Brasil (CAPES)–Finance Code 001. We also place the record thanks for the support of the Natural Sciences and Engineering Research Council of Canada (NSERC) and the funding from the Canada Research Chairs Program.