To investigate the influence of Ag and the loading of Ni species, Ni-Ag type catalysts were synthesized with varying Ni/Ag ratios (1, 1.5 and 2) using the coprecipitation method. The catalysts were extensively characterized using various techniques such as TG-DSC-SM, XRD, ICP, BET, SEM-EDX and TPR and subsequently tested in the CH₄/CO₂ reaction without any pretreatment. Regardless of the ratio employed, a phase mixture containing NiO and Ag was observed after calcination under air between 600 °C and 1200 °C. SEM analysis confirmed the presence of a close interface between Ag and NiO. The specific surface area was found to be significantly higher for the catalyst with lower Ni content (R = 1). TPR analysis demonstrated that the inclusion of Ag facilitated the reduction of Ni at lower temperatures. XRD analyses of the spent catalyst confirmed catalyst reduction during the reaction. Among the samples, a catalyst with Ni/Ag = 1 exhibited superior catalytic activity without any pretreatment under a reduction atmosphere, in which case the conversions of methane and CO₂ at 650 °C amounted to 38 and 45 mol%, respectively, with H₂/CO = 0.7 and 71 mol% of H₂. The presence of Ag species enhances the stability of the Ni catalyst and improves catalytic performance in the dry reforming of methane.

CuM and AgM (M = Cr, Fe) catalysts were synthesized, characterized, and evaluated in methane reforming with CO₂ with and without pretreatment under a H₂ atmosphere. Their textural and structural characteristics were evaluated using various physicochemical methods, including XRD, B.E.T., SEM-EDS, XPS, and H₂-TPR. It was shown that the nature of the species has a significant effect on these structural, textural, and reactivity properties. AgCr catalysts, presenting several oxidation states (Ag⁰, Ag⁺¹, Cr³⁺, and Cr⁶⁺ in Ag, AgCrO₂, and AgCr₂O₄), showed the most interesting catalytic performance in their composition. The intermediate Cr₂O₃ phase, formed during the catalytic reaction, played an important role as a catalytic precursor in the in situ production of highly dispersed nanoparticles, being less prone to coke formation in spite of the severe reaction conditions. In contrast, the AgFe catalyst showed low activity and a low selectivity for DRM in the explored temperature range, due to a significant contribution of the reverse water–gas shift reaction, which accounted for the low H₂/CO ratios.