Air- and water-stable and photocatalytically active germanium-based 2D perovskites by organic spacer engineering

Lidia Romani; Andrea Speltini; Rossella Chiara; Marta Morana; Clarissa Coccia; Costanza Tedesco; Vincenza Armenise; Silvia Colella; Antonella Milella; Andrea Listorti; Antonella Profumo; Francesco Ambrosio; Edoardo Mosconi; Riccardo Pau; Federico Pitzalis; Angelica Simbula; Damiano Ricciarelli; Michele Saba; Maria Medina-Llamas; Filippo De Angelis; Lorenzo Malavasi

doi:10.1016/j.xcrp.2022.101214

Air- and water-stable and photocatalytically active germanium-based 2D perovskites by organic spacer engineering

Cell Rep Phys Sci. 2023 Jan 18;4(1):101214. doi: 10.1016/j.xcrp.2022.101214.

Authors

Lidia Romani^{1

2}, Andrea Speltini¹, Rossella Chiara¹, Marta Morana¹, Clarissa Coccia¹, Costanza Tedesco¹, Vincenza Armenise³, Silvia Colella⁴, Antonella Milella³, Andrea Listorti³, Antonella Profumo¹, Francesco Ambrosio^{5

6

7}, Edoardo Mosconi⁷, Riccardo Pau^{8

9}, Federico Pitzalis⁸, Angelica Simbula⁸, Damiano Ricciarelli¹⁰, Michele Saba⁸, Maria Medina-Llamas^{1

10}, Filippo De Angelis^{7

11

12}, Lorenzo Malavasi¹

Affiliations

¹ Department of Chemistry and INSTM, University of Pavia, Via Taramelli 16, 27100 Pavia, Italy.
² Tecnologie di Generazione e Materiali, Ricerca sul Sistema Energetico - RSE S.p.A., Via Rubattino 54, 20134 Milano, Italy.
³ Department of Chemistry, University of Bari "Aldo Moro," via Orabona 4, 70126 Bari, Italy.
⁴ National Research Council, Institute of Nanotechnology (CNR-NANOTEC), c/o Department of Chemistry, University of Bari "Aldo Moro," via Orabona 4, 70126 Bari, Italy.
⁵ Dipartimento di Scienze, University of Basilicata, Viale dell'Ateno Lucano, 10, 85100 Potenza, Italy.
⁶ Department of Chemistry and Biology "A. Zambelli," University of Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, Salerno, Italy.
⁷ Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), Istituto CNR di Scienze e Tecnologie Chimiche "Giulio Natta" (CNR-SCITEC), via Elce di Sotto 8, 06123 Perugia, Italy.
⁸ Department of Physics, University of Cagliari, Cittadella Universitaria S.P. Monserrato-Sestu km 0.7, 09042 Monserrato, Italy.
⁹ Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 09747 Groningen, the Netherlands.
¹⁰ Unidad Académica Preparatoria, Plantel II, Universidad Autónoma de Zacatecas, Zacatecas, Zacatecas 98068, México.
¹¹ Department of Chemistry, Biology and Biotechnology, University of Perugia, via Elce di Sotto 8, 06123 Perugia, Italy.
¹² Department of Natural Sciences & Mathematics, College of Sciences & Human Studies, Prince Mohammad Bin Fahd University, Dhahran 34754, Saudi Arabia.

Abstract

There is increasing interest in the role of metal halide perovskites for heterogeneous catalysis. Here, we report a Ge-based 2D perovskite material that shows intrinsic water stability realized through organic cation engineering. Incorporating 4-phenylbenzilammonium (PhBz) we demonstrate, by means of extended experimental and computational results, that PhBz₂GeBr₄ and PhBz₂GeI₄ can achieve relevant air and water stability. The creation of composites embedding graphitic carbon nitride (g-C₃N₄) allows a proof of concept for light-induced hydrogen evolution in an aqueous environment by 2D Ge-based perovskites thanks to the effective charge transfer at the heterojunction between the two semiconductors.

Keywords: computational modeling; germanium perovskites; hydrogen generation; metal halide perovskites; photocatalysis.