This research discusses the CO2 valorization via hydrogenation over the non-noble metal clusters of Ni and Cu supported on graphitic carbon nitride (g-C3N4). The Ni and Cu catalysts were characterized by conventional techniques including XRD, AFM, ATR, Raman imaging, and TPR and were tested via the hydrogenation of CO2 at 1 bar. The transition-metal-based catalyst designed with atom-economy principles presents stable activity and good conversions for the studied processes. At 1 bar, the rise in operating temperature during CO2 hydrogenation increases the CO2 conversion and the selectivity for CO and decreases the selectivity for methanol on Cu/CN catalysts. For the Ni/CN catalyst, the selectivity to light hydrocarbons, such as CH4, also increased with rising temperature. At 623 K, the conversion attained ca. 20%, with CH4 being the primary product of the reaction (CH4 yield >80%). Above 700 K, the Ni/CN activity increases, reaching almost equilibrium values, although the Ni loading in Ni/CN is lower by more than 90% compared to the reference NiREF catalyst. The presented data offer a better understanding of the effect of the transition metals' small metal cluster and their coordination and stabilization within g-C3N4, contributing to the rational hybrid catalyst design with a less-toxic impact on the environment and health. Bare g-C3N4 is shown as a good support candidate for atom-economy-designed catalysts for hydrogenation application. In addition, cytotoxicity to the keratinocyte human HaCaT cell line revealed that low concentrations of catalysts particles (to 6.25 μg mL-1) did not cause degenerative changes.

Chemistry Innovation Research Center R and D Jubilant Biosys Knowledge Park 2 Greater Noida Uttar Pradesh 201310 India

Department of Chemistry College of Science King Saud University P O Box 2455 Riyadh 11451 Saudi Arabia

Department of Industrial and Engineering Chemistry Institute of Chemical Technology Mumbai Marathwada Campus Jalna 431 203 India

Independent Unit of Spectroscopy and Chemical Imaging Medical University of Lublin Chodzki 4a 20 093 Lublin Poland

Institute of Physical Chemistry Polish Academy of Science Kasprzaka 44 52 01 224 Warsaw Poland

Nanotechnology Centre Centre of Energy and Environmental Technologies VŠB Technical University of Ostrava 17 listopadu 2172 15 708 00 Ostrava Poruba Czech Republic

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Slechtitelu 27 77900 Olomouc Czech Republic

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