In this report, we have applied a facile, ligand-free, ambient synthesis protocol toward the fabrication of not only a series of lead-free Ge-based perovskites with the general formulation of MA1–xFAxGeI3 (where x was changed from 0, 0.25, 0.5, 0.75, to 1) but also CsGeI3. Specifically, our methodology for producing ABX3 systems is generalizable, regardless of the identity of either the A site cation or the X site halide ion. Moreover, it incorporates many advantages, including (i) the possibility of efficiently generating pure Ge-based perovskite particles of any desired chemical composition, (ii) the use of readily available, commercial precursors and comparatively lower toxicity solvents, (iii) the practicality of scale up, and (iv) the elimination of the need for any superfluous organic surface ligands or surfactants. In addition to providing mechanistic insights into their formation, we have examined the chemical composition, crystallite size, morphology, surface attributes, oxidation states, and optical properties of our as-prepared perovskites using a combination of diffraction, microscopy, and spectroscopy techniques. Specifically, we noted that the optical band gap could be reliably tuned as a function of chemical composition, via the identity of the A site cation. Moreover, we have probed their stability, not only under standard storage conditions but also, for the first time, when subjected to both e-beam- and X-ray-induced degradation, using cumulative data from sources such as synchrotron-based scanning hard X-ray microscopy. Importantly, of relevance for the potential practical incorporation of these Pb-free perovskites, our work has emphasized the possibility of controlling the chemical composition within Ge-based perovskites as a means of rationally tuning their observed band gaps and optical behavior.

The rational synthesis of Cu@TiO2 core@shell nanowire (NW) structures was thoroughly explored using a microwave-assisted method through the tuning of experimental parameters such as but not limited to (i) controlled variation in molar ratios, (ii) the effect of discrete Ti precursors, (iii) the method of addition of the precursors themselves, and (iv) time of irradiation. Uniform coatings were obtained using Cu/Ti molar ratios of 1:2, 1:1, 2:1, and 4:1, respectively. It should be noted that although relative molar precursor concentrations primarily determined the magnitude of the resulting shell size, the dependence was nonlinear. Moreover, additionally important reaction parameters, such as precursor identity, the means of addition of precursors, and the reaction time, were individually explored with the objective of creating a series of optimized reaction conditions. As compared with Cu NWs alone, it is evident that both of the Cu@TiO2 core–shell NW samples, regardless of pretreatment conditions, evinced much better catalytic performance, up to as much as 20 times greater activity as compared with standard Cu NWs. These results imply the significance of the Cu/TiO2 interface in terms of promoting CO2 hydrogenation, because TiO2 alone is known to be inert for this reaction. Furthermore, it is additionally notable that the N2 annealing pretreatment is crucial in terms of preserving the overall Cu@TiO2 core@shell structure. We also systematically analyzed and tracked the structural and chemical evolution of our catalysts before and after the CO2 reduction experiments. Indeed, we discovered that the core@shell wire motif was essentially maintained and conserved after this high-temperature reaction process, thereby accentuating the thermal stability and physical robustness of our as-prepared hierarchical motifs.

EDS and EXAFS spectroscopy are used as complementary techniques to investigate the local structure of bimetallic ultrathin nanowires. Results highlight the importance of using a combined approach to achieve an accurate understanding of these systems.