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Seeking alternatives to noble metals-based electrocatalysts for oxygen reduction reaction (ORR), hollow carbon spheres (CSs) were finely tuned with stable single-atom Fe–N species through a synthesis methodology requiring only earth-abundant metal precursors. CSs with different sizes were synthesized by sol-gel polycondensation of resorcinol with formaldehyde over silica nanoparticles, followed by thermal annealing and silica etching. A catalyst screening revealed the positive impact of both the hollow core and structural defects of the CSs for ORR. Single-atom Fe–N active sites were introduced on the best performing CSs through simultaneous incorporation of iron and nitrogen precursors, and glucose. A significant enhancement in ORR activity was observed despite the small iron load introduced (0.12 wt%). ORR performance indicators, advanced characterization, and molecular simulation studies revealed nitrogen's crucial role in anchoring individual iron atoms and modulating the charge density nearby the active sites (increase of 80 mV in the half-wave potential). Adding glucose as a chelating agent enhances the metal-heteroatom coordination and subsequent dispersion of iron, accounting for an increase of 20 mV in the half-wave potential, an average of electrons transferred as high as 3.9 (at 0.4 V vs. RHE), and higher stability (99%) than that of a platinum-based (20 wt%) electrocatalyst (92%).

A comprehensive study was conducted on the synthesis of Cu-MnOx catalysts using a one-pot hydrothermal method followed by a calcination step. These catalysts were thoroughly characterized using techniques such as X-ray diffraction (XRD), X-ray fluorescence (XRF), N2 physisorption, X-ray photoelectron spectroscopy (XPS), temperature programmed desorption and reduction (TPD and TPR), and advanced transmission electron microscopy (TEM). The results revealed that the Cu:Mn molar ratio of the precursors, Cu(NO3)2 and KMnO4, had a significant impact on the crystalline structure and morphology of the synthesized samples. A Cu-doped cryptomelane with a nanorod morphology was observed when the Cu:Mn molar ratio was 0.05. Conversely, a mixture of Cu-doped cryptomelane nanorods, Mn2O3, and Cu1.5Mn1.5O4 spinel nanoparticles was formed at molar ratios of 0.1 and 0.25. The catalytic activities of these catalysts for CO oxidation followed the order: 0.25Cu-MnOx ≈ 0.1Cu-MnOx > 0.05Cu-MnOx > cryptomelane. A good correlation was found between the catalytic performance and reducibility of the catalysts under CO atmosphere that can be related to the ability of the samples to activate the CO molecule. The high reducibility of the sample even at room temperature suggest that the CO oxidation over the synthesized Cu-MnOx catalysts may follow a Mars van Krevelen model.

Methanol adsorption over both supported NiSn Nps and analogous NiSn catalyst prepared by impregnation was studied by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to gain insights into the basis of hydrogen production from methanol steam reforming. Different intermediate species such as methoxides with different geometry (bridge and monodentate) and formate species were identified after methanol adsorption and thermal desorption. It is proposed that these species are the most involved in the methanol steam reforming reaction and the major presence of metal-support interface sites in supported NiSn Nps leads to higher production of hydrogen. On the basis of these results, a plausible reaction mechanism was elucidated through the correlation between the thermal stability of these species and the evolution of the effluent gas released. In addition, it was demonstrated that DME is a secondary product generated by condensation of methoxides over the acid sites of alumina support in an acid-catalyzed reaction.

Intermetallic compounds (IMCs) are interesting materials in the field of heterogeneous catalysis due to their ordered structure and tunable electronic properties. These IMCs can act as precursor to synthesize metal/metal oxide composite catalysts that are more active than just the starting IMCs. In this work, Sm2Co7 and SmCo5 IMCs were used as precursors to prepare highly active and stable Co_SmO, Co_Sm2O3 and Co3O4_Sm2O3 catalysts via controlled modification. Transmission electron microscopy (TEM) demonstrated that Co and Sm2O3 Nano crystallites were formed after the modification of the starting IMC. IMCs derived Co_SmO and Co_Sm2O3 were stable and active in NH3 synthesis with very low activation energy of 55 and 77 kJ/mol respectively. The structural, morphological and surface characterization revealed that a strong metal support interaction existed between Co and Sm2O3 (electronic effect) along with the presence of surface steps and edges of Co nano crystallites (structural effect) that activated the N2 at low temperature (360 °C). Similarly, Co3O4_Sm2O3 derived from the IMC were found to exhibit high CO2 and butane conversion in butane dry reforming at low temperature (550 °C) with excellent stability. The study revealed that the presence of Co3O4 and Sm2O3 active sites in close proximity (geometrical effect) promoted the simultaneous adsorption or activation of butane and CO2. The Co_Sm2O3 and Co3O4_Sm2O3 derived from IMCs exhibited superior catalytic performance in both NH3 synthesis and butane dry reforming compared to similar compositional catalyst synthesized by hydrothermal route. These studies pave the way to potential uses of IMCs as precursors to derive composite metal/metal oxide catalysts that are highly stable and active despite their low surface areas.