An efficient strategy for the enhancement of adsorptivity of microporous carbons against gaseous formaldehyde: Surface modification with aminosilane adducts

摘要

In an effort to develop a cost-effective mitigation tool for volatile organic compounds, particularly formaldehyde (FA), microporous activated carbon (AC) was modified into three different forms of AC-1, AC-2, and AC-3 using a raw commercial AC product (AC-0). First, AC-1 and AC-2 were produced by the modification of AC-0 with N/S heteroatoms using identical mixture of dicyandiamide and thiourea precursors through either solvothermal (AC-1) or microwave-assisted calcination (AC-2) synthesis. Second, aminosilane-functionalized AC (AC-3) was prepared solvothermally using N-[3-(Trimethoxysilyl)propyl]ethylenediamine reagent. The relative adsorption performances for gaseous FA (1 ppm) in terms of 10% breakthrough volume (BTV10: L atm g~(-1)) at near-ambient conditions (25 °C and 1 atm) were AC-3 (132) > AC-2 (66.5) > AC-1 (14.2) > AC-0 (10.4). In a comparison based on partition coefficients (mole kg~(-1) Pa~(-1)) at BTV10, AC-3 outperformed AC-0 by a factor of 214, while the adsorption performance of AC-2 was 36-times higher than AC-1. The enhanced performance of AC-2 over AC-1 reflected the effect of the microwave synthesis protocol on the improvement of surface chemistry (e.g., N/S doping) and texture (e.g., surface area and pore volume) of AC-based adsorbents as compared to conventional solvothermal method. Further, the prominent role of surface chemistry (e.g., relative to textural properties), as observed with the increases in the amount of doped functional elements (including N:C and silicon:C ratios), is supported by the apparent dependence of performance on the selected modification procedures. Based on kinetic and X-ray photoelectron spectroscopy analyses, the superiority of aminosilylated AC-3 can be attributed to a synergistic effect between physisorption (e.g., pore diffusion) and chemical interactions of the FA carbonyl (C=0) group with amine and silica functionalities (via Mannich coupling [Schiff base] and cycloaddition reaction mechanisms, respectively). This confirms the significance of surface chemistry, relative to pore diffusion, in achieving maximum adsorption of gaseous FA molecules.