A metal–organic framework modulated to site-isolate Cl˙ pendants via radical inter-conversion for degrading hard-to-ionize aqueous organic wastes

Abstract

Compared with conventional •OH, Cl• is longer-lived, more selective to destabilize refractory electron (e-)-donating aqueous aromatics via radicalization, and renewable via e- transfer from aromatics to enable Cl•↔Cl- inter-conversion. To...

Unveiling the Catalytic Merits of LaV3O9 over Conventional LaVO4 Polymorphs to Boost Desired Kinetics of Humid NOX Reduction and Poison Disintegration

“…Meanwhile, all of the catalysts were subjected to CO isotherm experiments at 35 °C (near 25 °C) to quantify the numbers of CO-accessible LA sites included in a per-gram of the catalysts (N CO ) at 1 bar (Figure S8 and Table S2). ,,− The N CO values of t -LaV/ m -LaV (4.5–4.8 μmol CO g CAT –1 ) were around 2.5-fold greater than those of LaV 3 /LaV 3 -Sb. This was in accordance with the amounts of open V 5+ species contained in a per-gram of the catalysts, which were anticipated based on the V 5+ species of the [V 5+ -(O 2– ) 4 ] 3– /[V 5+ -(O 2– ) 5 ] 5– subunits for polymorphic LaVO 4 /LaV 3 O 9 , as stated in the Introduction. − As predicted, the N CO values of the catalysts subjected to SO Z 2– modification were reduced to between a half and two-thirds of those for the as-synthesized catalysts, as was the case with the CO-accessible BET surface areas (S BET, CO ) of the catalysts prior and post SO Z 2– functionalization (Table S2).…”

“…It was reported that the BA – -H + , O L , and O V species of the SO Z 2– -modified catalysts are prone to binding with H 2 O via (pseudo-) hydrogen bond formation and thus can moderately limit their accessibilities to NH 3 , NO X , and O 2 , respectively, under a wet gas feed. − To compare the H 2 O-accessible BET surface areas (S BET, H2O ) of the catalysts and their binding intimacy with H 2 O, the H 2 O isotherms of the catalysts were collected at 10–40 °C and fitted using the Toth equation (Figure S15 and Table S10). ,,,− The resulting H 2 O isotherms were then simulated to evaluate the isosteric heats of H 2 O adsorption (E H2O ) for the catalysts at near-zero H 2 O coverages via the Clausius–Clapeyron equation, as depicted in the Supporting Information. ,,,− The S BET, H2O values of the catalysts at 40 °C were similar to the exception of t -LaV-S (S BET, H2O of 28.4 m H 2 O 2 g CAT –1 for t -LaV-S; 12.9–13.4 m H 2 O 2 g CAT –1 for the others; Table S2). This partially matched the trend of H 2 O binding affinities for the catalysts, while potentially demonstrating the sixth merit of LaV 3 O 9 in enhancing the H 2 O resistance over the LaVO 4 polymorphs.…”