Engineering polyhedral high entropy oxide with high-index facets via mechanochemistry-assisted strategy for efficient oxidative desulfurization.

High entropy oxides are promising catalysts for numerous catalytic oxidation processes with oxygen as the oxidant. However, most of them often show bulk morphologies, which hinders the full exposure of active sites. In this work, a unique 26-faceted polyhedral high entropy oxide MnNiCuZnCoOx-1000 (P-HEO) with highly active site exposure is fabricated via a mechanochemistry-assisted strategy. By employing such a strategy, the supersaturation of P-HEO during the crystal growth process is effectively reduced to form high-index facets, which is proved to be beneficial to the formation of high-index facets. Characterization results indicate that more oxygen vacancies are generated in P-HEO compared with the bulk counterparts. Density functional theory calculations reveal that the high-index facets {-211} can facilitate adsorption and activation of O2 because of the higher adsorption energy -2.23 eV compared with that of (111) surfaces (-1.79 eV), which induces significantly enhanced activity for organic sulfides oxidation. Interestingly, the synthesized P-HEO with high-index facets shows a 98.4% removal rate of dibenzothiophene from model oil within 8 h at 120 °C, which is much higher than that of the bulk counterparts (33.5%).

Hierarchical porous boron nitride with boron vacancies for improved adsorption performance to antibiotics.

Designing atomically defective adsorbents with high specific surface area has emerged as a promising approach to improve sorption properties. Herein, hierarchical porous boron nitride nanosheets with boron vacancies (Bv-BNNSs) were in-situ synthesized via a one-step ZnCl2-assisted strategy. Being benefitted from the dual-functional template of zinc salt, highly-active boron vacancies and abundant hierarchical pores were simultaneously generated in the Bv-BNNSs framework. By employing the boron vacancies engineering strategy, the morphological and electronic structures were controllably tuned. Meanwhile, the specific surface area was improved to as high as 1104 m2/g. Owning to the abundance of accessible surface active-sites, the sorption capacity to antibiotic tetracycline (TC) on Bv-BNNSs was boosted by 38% compared to the pristine boron nitride nanosheets (BNNSs). Detailed fitting results showed that TC sorption on Bv-BNNSs obeyed the pseudo-second order kinetic equation and the Freundlich isotherm model. The pi - pi interaction with a multi-layered stacking form was proposed as the dominated sorption mechanism. Furthermore, DFT calculations verified that the interaction energy between Bv-BNNSs and TC was enhanced. The high activity, excellent selectivity, and remarkable durability of the Bv-BNNSs nanomaterial suggest the great potential in practical wastewater treatment.

Synthesis of Porous Sulfonamide Polymers by Capturing Atmospheric Sulfur Dioxide.

The emission of SO2 from the burning of fossil fuel has resulted in a severe atmospheric pollution. The development of efficient strategies for not only capturing but also utilizing SO2 is highly welcome. A simple, mild, and versatile method has been developed that exploits atmospheric SO2 in the synthesis of porous polymers. Inspired by the chemistry of sulfonamides, contorted or bulky monomers with multiple amine groups were cross-linked by SO2 molecules in the presence of Et3 N and I2 . The sulfonamide polymers have specific surface areas up to 211 m2 g-1 . In contrast to most porous polymers, the porous sulfonamide polymers (PSPs) are soluble in organic solvents, thus offering a chance to study their structures and molecular weights by liquid-state NMR spectroscopy and gel-permeation chromatography, respectively. Moreover, these PSPs can be easily processed into organic membranes. The current concept should encourage more studies to design porous polymers with SO2 or CO2 gases as linkages.

Highly Efficient Carbon Monoxide Capture by Carbanion-Functionalized Ionic Liquids through C-Site Interactions.

A novel method for the highly efficient and reversible capture of CO in carbanion-functionalized ionic liquids (ILs) by a C-site interaction is reported. Because of its supernucleophilicity, the carbanion in ILs could absorb CO efficiently. As a result, a relatively high absorption capacity for CO (up to 0.046 mol mol-1 ) was achieved under ambient conditions, compared with CO solubility in a commonly used IL [Bmim][Tf2 N] (2×10-3  mol mol-1 ). The results of quantum mechanical calculations and spectroscopic investigation confirmed that the chemical interaction between the C-site in the carbanion and CO resulted in the superior CO absorption capacities. Furthermore, the subsequent conversion of captured CO into valuable chemicals with good reactivity was also realized through the alkoxycarbonylation reaction under mild conditions. Highly efficient CO absorption by carbanion-functionalized ILs provides a new way of separating and converting CO.

Multi-Molar Absorption of CO2 by the Activation of Carboxylate Groups in Amino Acid Ionic Liquids.

A new strategy for multi-molar absorption of CO2 is reported based on activating a carboxylate group in amino acid ionic liquids. It was illustrated that introducing an electron-withdrawing site to amino acid anions could reduce the negative inductive effect of the amino group while simultaneously activating the carboxylate group to interact with CO2 very efficiently. An extremely high absorption capacity of CO2 (up to 1.69 mol mol(-1) ) in aminopolycarboxylate-based amino acid ionic liquids was thus achieved. The evidence of spectroscopic investigations and quantum-chemical calculations confirmed the interactions between two kinds of sites in the anion and CO2 that resulted in superior CO2 capacities.

Rational design and synthesis of a porous, task-specific polycarbazole for efficient CO2 capture.

We present a rational design and synthesis of a novel porous pyridine-functionalized polycarbazole for efficient CO2 capture based on the density functional theory calculations. The task-specific polymer, generated through a one-step FeCl3-catalyzed oxidative coupling reaction, exhibits a superior CO2 uptake at 1.0 bar and 273 K (5.57 mmol g(-1)).