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Progressive research on reducing engine emissions is highly valued due to the emissions’ significant environmental and health impacts. This comprehensive comparative study examines the catalytic efficiency of manganese (Mn) and cerium silica (Ce-Si) synthesis catalyst-based molds in a diesel engine using a selective catalytic reduction (SCR) technique with diesel and diesel–plastic oil blend (DPB) (B50). In addition to Fourier transform infrared spectroscopy (FTIR) studies, X-ray diffraction (XRD), scanning electron microscopy (SEM), and the Brunauer–Emmett–Teller (BET) method are utilized to characterize the produced molds before and after exhaust gas passes. The Ce-Si-based mold demonstrates superior redox capacity, better adsorption capacity, and better thermal stability, attributed to enhanced oxygen storage and structural integrity compared to the Mn-based mold. Under minimum load conditions, nitrogen oxide (NO) reduction efficiency peaks at 80.70% for the Ce-Si-based mold in the SCR treatment with DPB fuel. Additionally, significant reductions of 86.84%, 65.75%, and 88.88% in hydrocarbon (HC), carbon monoxide (CO), and smoke emissions, respectively, are achieved in the SCR treatment under optimized conditions. Despite a wide temperature range, Ce-Si-based mold promotes high surface area and superior gas diffusion properties. Overall, the Ce-Si-based mold provides efficient emission control in diesel engines, which paves a path for developing better environmental sustainability. The outcomes contribute to advancing environmental sustainability by supporting the achievement of SDGs 7, 11, and 13. Full article