Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)
DOI: https://doi.org/10.29363/nanoge.matsus.2023.068
Publication date: 18th July 2023
Transition metal (TM) nitrides are an emerging class of catalytic and photoelectrocatalytic materials.[1],[2] In general, nitrogen-poor TM nitrides are usually refractory materials with metallic character while nitrogen-rich nitrides often possess semiconducting character.[3] Hence, while the former are potential electrocatalyst candidates, the latter may qualify as photoelectrode absorber materials. For example, ZrN has recently been proposed as an electrocatalyst for both the electrochemical nitrogen[4] and oxygen[5] reduction reactions (ORR and NRR), while Zr3N4 and also Zr2N2O have been suggested as potential photoanode materials in photoelectrochemical water oxidation.[2] In this contribution, we test these hypotheses regarding the (photo)electrochemical characteristics of Zr-based (oxy)nitrides by experiment. To this end, we investigate reactively sputtered thin films for the electrochemical NRR/ORR and the photoelectrochemical oxygen evolution reaction (OER). Previous experiments on Ta-based nitrides have shown that addition of oxygen during the reactive sputter process is necessary to access higher metal oxidation states.[6] Indeed, as we introduce controlled amounts of oxygen at otherwise fixed deposition conditions, we observe a transition from metallic ZrN to a disordered nitrogen-rich ZrxNy to a crystalline bixbyite-type Zr2N2O to nitrogen-doped cubic ZrO2. Crystalline Zr3N4 was not accessible under the used experimental conditions. While we observe a lack of electrocatalytic activity for ZrN in NRR and ORR and instabilities of the disordered nitrogen-rich ZrxNy in the photoelectrochemical OER, introducing more oxygen into the structure leads to a more stable crystalline structure (Zr2N2O), the opening of a band gap in the visible range, and the emergence of photoelectrochemical activity for oxidation reactions. Based on chopped linear sweep voltammetry measurements, we show that Zr2N2O films are photoactive for the OER in alkaline electrolyte with low onset potentials, indicating an overall favorable band alignment of the material with respect to the water oxidation and reduction potentials. While the observed photocurrents are still significantly lower than for the benchmark oxynitride TaON, further material optimization could potentially close this gap and provide a materials system functioning as sustainable photoanode.
This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 864234), from Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany´s Excellence Strategy – EXC 2089/1 – 390776260, and TUM.Solar in the context of the Bavarian Collaborative Research Project Solar Technologies Go Hybrid (SolTech). J.E. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – 428591260 and support from the Bavarian Academy of Sciences and Humanities. S.S. acknowledges support from the Alexander von Humboldt Foundation.