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Taking advantage of tungsten oxide inherent Brønsted–Lewis acidity, the first series of WO3–SiO2(HIPE) monolithic (MUB-104(x) series) catalysts bearing multiscale porosity have been designed through integrative chemistry. At the microscopic length scale, beyond X-ray diffraction (XRD) revealing the WO3monoclinic structure, local electron spin resonance (ESR) spectroscopy addresses g values clearly located at the frontier between extended WO3phases and polyanion clusters, in agreement with scanning transmission electron microscopy high-angle annular dark field (STEM-HAADF) investigations. NH3-TPD shows that when the tungsten loading is increased from 10 wt % for MUB-104(1) to 24 wt % for MUB-104(3), the amount of acidic sites significantly decreases from 0.35 to 0.08 mmol of NH3g–1, respectively, in agreement with the particle sizes. The MUB-104(x) series offers efficient cosolvent-less heterogeneous cycling catalysis toward both Friedel–Crafts alkylation and acylation syntheses. MUB-104(1) carries the highest turnover number (TON) of 121 and turnover frequency (TOF) of 20 h–1, while for acylation, MUB-104(1) carries the highest TON of 117 and TOF of 26 h–1. Besides, we find out that the catalysts offer good selectivity, where 30/70% of ortho- and para-substituted alkylated products are obtained. Considering the acylation reaction, the selectivity is even higher, reaching 100% toward the para-substituted acylated product. The catalyst, due to its intrinsic monolithic character, can be easily extracted from the reactive media, recycled, and re-employed further.

In the general context of environmental air remediation, copper-oxide-based self-standing porous catalysts (MUB-103(x)) and their reduced homologues (Red MUB-103(x)) have been synthesized and studied for the thermoconversion of CO to CO2. Catalytic experiments under dry air conditions reveal that for nonreduced catalysts, increasing the Cu content diminishes the light-off temperature T50(corresponding to 50% conversion). The catalytic performances exhibited by the CuO phase dispersed in the silica pores of MUB-103(x) samples are the highest reached to date despite the limitations of the experimental conditions used. After reduction with H2, the native Red MUB-103(x) catalysts offer CO conversion efficiencies significantly more increased, leading to a lowering of the T50values equal to at least 100°C. As such, the CO conversion reaches a T50value of 160 °C for Red MUB-103(2) with 1.81 wt % Cu; this catalyst displays a specific rate of 8.6 mmolCOgCu–1s–1at 175 °C, largely higher than those observed to date. The performances of the Red MUB-103(2) sample were evaluated for CO oxidation under humid conditions with the addition of 5 vol % water vapor in the feed during four cycles, leading to the same efficiency when compared with that under dry experimental conditions, revealing robustness. A drastic increase in the CO conversion temperature was observed for the 4th cycle, i.e., after 8 h under humid conditions. Analyses of the spent Red MUB-103(2) catalyst after four cycles reveal a slight oxidation of copper, leading to Cu2O species. Importantly, after four cycles, the deactivated catalyst was able to partially recover its performance when reactivated through a 2 h reducing treatment under H2at 400 °C.