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Carbon capture and sequestration from point sources is an important component in the CO2 emission mitigation portfolio. In particular, sorbents with both high capacity and selectivity are required for reducing the cost of carbon capture. Although physisorbents have the advantage of low energy consumption for regeneration, it remains a challenge to obtain both high capacity and sufficient CO2/N2 selectivity at the same time. Here, we report the controlled synthesis of a novel N-doped hierarchical carbon that exhibits record-high Henry's law CO2/N2 selectivity among physisorptive carbons while having a high CO2 adsorption capacity. Specifically, our synthesis involves the rational design of a modified pyrrole molecule that can co-assemble with the soft Pluronic template via hydrogen bonding and electrostatic interactions to give rise to mesopores followed by carbonization. The low-temperature carbonization and activation processes allow for the development of ultrasmall pores (d < 0.5 nm) and preservation of nitrogen moieties, essential for enhanced CO2 affinity. Furthermore, our described work provides a strategy to initiate developments of rationally designed porous conjugated polymer structures and carbon-based materials for various potential applications.

Porous graphitic carbon is essential for many applications such as energy storage devices, catalysts, and sorbents. However, current graphitic carbons are limited by low conductivity, low surface area, and ineffective pore structure. Here we report a scalable synthesis of porous graphitic carbons using a conjugated polymeric molecular framework as precursor. The multivalent cross-linker and rigid conjugated framework help to maintain micro- and mesoporous structures, while promoting graphitization during carbonization and chemical activation. The above unique design results in a class of highly graphitic carbons at temperature as low as 800 °C with record-high surface area (4073 m2 g–1), large pore volume (2.26 cm–3), and hierarchical pore architecture. Such carbons simultaneously exhibit electrical conductivity >3 times more than activated carbons, very high electrochemical activity at high mass loading, and high stability, as demonstrated by supercapacitors and lithium–sulfur batteries with excellent performance. Moreover, the synthesis can be readily tuned to make a broad range of graphitic carbons with desired structures and compositions for many applications.

Adsorption of interfacially active components at the water/oil interface plays critical roles in determining the properties and behaviors of emulsion droplets. In this study, the droplet probe atomic force microscopy (AFM) technique was applied, for the first time, to quantitatively study the interaction mechanism between water-in-oil (W/O) emulsion droplets with interfacially adsorbed asphaltenes. The behaviors and stability of W/O emulsion droplets were demonstrated to be significantly influenced by the asphaltene concentration of organic solution where the emulsions were aged, aging time, force load, contact time, and solvent type. Bare water droplets could readily coalesce with each other in oil (i.e., toluene), while interfacially adsorbed asphaltenes could sterically inhibit droplet coalescence and induce interfacial adhesion during separation of the water droplets. For low asphaltene concentration cases, the adhesion increased with increasing asphaltene concentration (≤100 mg/L), but it significantly decreased at relatively high asphaltene concentration (e.g., 500 mg/L). Experiments in Heptol (i.e., mixture of toluene and heptane) showed that the addition of a poor solvent for asphaltenes (e.g., heptane) could enhance the interfacial adhesion between emulsion droplets at relatively low asphaltene concentration but could weaken the adhesion at relatively high asphaltene concentration. This work has quantified the interactions between W/O emulsion droplets with interfacially adsorbed asphaltenes, and the results provide useful implications into the stabilization mechanisms of W/O emulsions in oil production. The methodology in this work can be readily extended to other W/O emulsion systems with interfacially active components.

Co 3 O 4 is an attractive earth-abundant catalyst for CO oxidation, and its high catalytic activity has been attributed to Co 3+ cations surrounded by Co 2+ ions. Hence, the majority of efforts for enhancing the activity of Co 3 O 4 have been focused on exposing more Co 3+ cations on the surface. Herein, we enhance the catalytic activity of Co 3 O 4 by replacing the Co 2+ ions in the lattice with Cu 2+ . Polycrystalline Co 3 O 4 nanowires for which Co 2+ is substituted with Cu 2+ are synthesized using a modified hydrothermal method. The Cusubstituted Co 3 O 4 _Cux polycrystalline nanowires exhibit much higher catalytic activity for CO oxidation than pure Co 3 O 4 polycrystalline nanowires and catalytic activity similar to those single crystalline Co 3 O 4 nanobelts with predominantly exposed most active {110} planes. Our computational simulations reveal that Cu 2+ substitution for Co 2+ is preferred over Co 3+ both in the Co 3 O 4 bulk and at the surface. The presence of Cu dopants changes the CO adsorption on the Co 3+ surface sites only slightly, but the oxygen vacancy is more favorably formed in the bonding of Co 3+ −O−Cu 2+ than in Co 3+ −O−Co 2+ . This study provides a general approach for rational optimization of nanostructured metal oxide catalysts by substituting inactive cations near the active sites and thereby increasing the overall activity of the exposed surfaces. ■ INTRODUCTIONCarbon monoxide (CO) emission from transportation and industrial activities is harmful to both human health and the environment. Currently, CO emission is effectively reduced, mainly through catalytic oxidation over catalysts. 1−4 The most active catalysts for CO oxidation are noble metals, but they are expensive and are of limited supply. Co 3 O 4 has emerged as an attractive alternative catalyst for CO oxidation because of its optimal CO adsorption strength, low barrier for CO reaction with lattice O, and excellent redox capacity. 1,5−8 A breakthrough on Co 3 O 4 for catalytic CO oxidation showing that Co 3 O 4 nanorods with predominantly exposed {110} planes exhibit a much higher catalytic activity for CO oxidation and larger resistance to deactivation by water than Co 3 O 4 nanoparticles was reported by Xie et al. 9 The high catalytic activity of Co 3 O 4 {110} planes is attributed to its higher concentration of Co 3+ cations (correspondingly fewer Co 2+ cations) than other crystal planes, since only Co 3+ cations surrounded by Co 2+ ions are active for catalytic oxidation of CO. 10,11 Subsequently, a number of Co 3 O 4 nanostructures, ranging from nanobelts, nanospheres, nanocubes, and nanotubes to nanowires, have been synthesized with the purpose of preferentially exposing Co 3+ cations. 11−14 Nevertheless, regardless of the morphology of the Co 3 O 4 nanostructures, even the highly active Co 3 O 4 {110} planes still contain Co 2+ cations, which have been assumed to be inactive for catalytic oxidation of CO, 9−11 and ultimately limits the catalytic activity of Co 3 O 4 for CO oxidation. Therefore, substituting Co 2+ with...