Mn oxide is a particular class of
metal phase highly active in
reducing NO
X
or oxidizing NH3 at low temperatures yet needs amendment in terms of surface acidic/redox
sites to improve selectivities to desired N2 (S
N2) along with the promotion of SO2 tolerance.
This study reports the use of supercritical CO2 extraction
(SC-CO2) as a means to adjust the quantities/strengths
of surface sites present in the resulting Mn oxides on TiO2 (Mn-CO2) and validates the advantages of SC-CO2 with regard to mechanistic viewpoints via kinetic evaluation and
control reactions. SC-CO2 was demonstrated to promote the
activity or diversity of Langmuir–Hinshelwood-type or Eley–Rideal-type
NO
X
reduction pathways to produce N2 only. This was enabled by increasing the area of surface
sites accessible to NH3/NO
X
/O2 at ≤200 °C, as evidenced by a large NO
X
consumption rate and pre-factor of Mn-CO2 in addition to in situ DRIFT experiments.
In addition, SC-CO2 could tailor redox sites in such a
way as to circumvent an Eley–Rideal-type NO
X
reduction pathway to produce undesired NO2/N2O at 220–280 °C while detouring Langmuir–Hinshelwood-typed
NO
X
reduction to yield undesired products.
Furthermore, SC-CO2 could attenuate the Lewis acidic strength
of surface sites and therefore deterred NH3 oxidation at
up to ∼280 °C. Meanwhile, Mn-CO2 regulated
the formation of intermediates vital to direct NH3 consumption
rates (−r
NH3) and N2 selectivities in a desired manner at 280–400 °C. Hence,
Mn-CO2 provided higher S
N2 values
despite exhibiting smaller −r
NH3 values in comparison with those of the analogue unsubjected to SC-CO2 (Mn). The benefits provided by SC-CO2 were coupled
to enhance NO
X
reduction performance of
Mn-CO2 over Mn at 150–400 °C. Importantly,
Mn-CO2 enhanced long-term stability in reducing NO
X
over Mn in the presence of SO2 at
≤200 °C by encouraging the formation of Brönsted
acidic sites and hampering the transition of Lewis acidic Mn species
to MnSO3/MnSO4.