CeO2-based
catalysts are potentially suitable for H2S-selective oxidation,
but their practical application is
limited due to the problem of sulfate formation. Herein, we report
a facile citric acid-assisted hydrothermal process for the fabrication
of porous Fe-doped CeO2 with flower-like morphology that
can drastically promote the catalytic activities of CeO2 with high durability. Among the synthesized catalysts, the one with
well-defined (110) and (100) planes is highly active for H2S-selective oxidation with H2S conversion and sulfur selectivity
of almost 100% at 220 °C, superior to most of the reported Ce-based
catalysts. Meanwhile, outstanding catalytic stability is achieved
because the presence of Fe ions alleviates ceria deactivation due
to sulfation. The results of systematic investigation prove that the
doping of Fe not only raises the density of oxygen vacancies but also
promotes the redox ability and oxygen activity of the catalyst. We
conducted in situ DRIFTS (diffuse reflection infrared
Fourier transform spectroscopy) experiments and density functional
theory (DFT) calculations to disclose the reaction mechanism of H2S oxidation. The derived insights are important for the design
of efficient ceria-related catalysts for practical applications.
Classical amino-functionalized Fe-terephthalate metal-organic framework NH-MIL-53(Fe) and its parent framework MIL-53(Fe) were prepared via simple hydrothermal methods. The catalytic performaces of these two Fe-MOFs were explored for the selective oxidation of HS. The physicochemical properties of the fresh and used Fe-MOFs catalysts were investigated by XRD, BET, SEM, FT-IR, CO-TPD, and XPS techniques. It was found that the introduction of amino groups reduces the activation energies for HS oxidation and endows this catalyst surface with moderate basic sites. As a result, the NH-MIL-53(Fe) catalyst displays high HS conversion and near 100% S selectivity in the temperature range of 130-160 °C, outperforming commercial FeO and activated carbon. Moreover, a plausible reaction route for HS selective oxidation over NH-MIL-53(Fe) is proposed. This work opens up the possibility of utilizing MOFs as efficient catalyst for desulfuration reactions.
Direct catalytic
selective oxidation of H2S to sulfur
at low temperature has been drawing attention. Molybdenum carbide
(Mo2C), in which the excess occupied orbitals provide more
back-donation chances for the adsorbents’ π-orbitals,
shows activity in electrocatalysis, photocatalysis, thermocatalysis,
etc. that are comparable to those of noble metals. This work reports
for the time the use of Mo2C and Mo2C-modified
g-C3N4 for catalytic selective oxidative desulfurization.
The density functional theory calculation indicates that Mo2C facilitates the adsorption of H2S molecule and the HS
group. Furthermore, the Mo2C-modified g-C3N4 shows a sulfur yield of as high as 99.0% at 190 °C,
much higher than that of g-C3N4 (46.0%). The
good stability of the catalyst was demonstrated by X-ray diffraction,
Fourier transform infrared spectra, and so on. Remarkably, the H2S conversion of the Mo2C-modified g-C3N4 remains constant (95.0%) at 190 °C for as long
as 30 h. As a first demonstration using carbides in selective H2S oxidation, this work provides an opportunity to develop
a novel class of potential catalysts.
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