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The deactivation issue arising from alkali poisoning over catalysts is still a challenge for the selective catalytic reduction of NOx by NH3. Herein, improved NOx reduction in the presence of alkaline metals over phosphate-modified Fe2O3/TiO2 catalysts has been originally demonstrated via tailoring the reaction paths by in situ creating alkali-poisoning sites. The introduction of phosphate results in the partial formation of iron phosphate species and makes the catalyst to mainly exhibit the characteristics of FePO4, which is responsib