In this work, the effective ultra-deep catalytic adsorptive desulfurization (CADS) using Ti-silica gel adsorbent at low Ti loading range (< 1%) was investigated. The superior CADS capacity (37.3 mg-S/g-A) and high TOF value (432 h-1) for dibenzothiophene (DBT) were achieved at 0.6% of Ti loading with high dispersion and low Ti coordination. The catalytic oxidation of DBT conformed to the pseudo-first-order kinetic model, and the corresponding rate equation was well described as rDBT=[(N^2)*k/(K*[CHP])]*[DBT], where the TiOOR is determined as the intermediate to enable the DBT oxidation to the corresponding sulfone (DBTO2). The effectiveness of CADS using Ti-SG was verified in various real low-sulfur diesels with varied sulfur concentrations and O/S ratios in the dynamic fixed-bed adsorption and multi-cycle regenerations. This work provides insights on using low-cost bifunctional catalytic adsorbents at low Ti loading for effective CADS to realize ultra-deep desulfurization of transportation fuels.

We introduce a straightforward method for the preparation of novel starch-based ultramicroporous carbons (SCs) that demonstrate high CH4 uptake and excellent CH4/N2 selectivity. These SCs are derived from a combination of starch and 1-6 wt. % of acrylic acid, and the resulting materials are amenable to surface cation exchangeability as demonstrated by the formation of highly dispersed K+ in carbon precursors. Following activation, these SCs contain ultramicropores with narrow pore-size distributions of <0.7 nm, leading to porous carbon-rich materials that exhibit CH4 uptake values as high as 1.86 mmol/g at 100 kPa and 298 K, the highest uptake value for CH4 to date, with the IAST-predicted CH4/N2 selectivity up to 5.7. Both the potential mechanism for the formation of narrow pores and the origin of the favorable CH4 adsorption properties are discussed and examined. This work may potentially guide future designs for carbon-rich materials with excellent gas adsorption properties.