Balancing the Kinetic and Thermodynamic Synergetic Effect of Doped Carbon Molecular Sieves for Selective Separation of C2H4/C2H6.

Selective separation of ethylene and ethane (C2H4/C2H6) is a formidable challenge due to their close molecular size and boiling point. Compared to industry-used cryogenic distillation, adsorption separation would offer a more energy-efficient solution when an efficient adsorbent is available. Herein, a class of C2H4/C2H6 separation adsorbents, doped carbon molecular sieves (d-CMSs) is reported which are prepared from the polymerization and subsequent carbonization of resorcinol, m-phenylenediamine, and formaldehyde in ethanol solution. The study demonstrated that the polymer precursor themselves can be a versatile platform for modifying the pore structure and surface functional groups of their derived d-CMSs. The high proportion of pores centered at 3.5 Å in d-CMSs contributes significantly to achieving a superior kinetic selectivity of 205 for C2H4/C2H6 separation. The generated pyrrolic-N and pyridinic-N functional sites in d-CMSs contribute to a remarkable elevation of Henry selectivity to 135 due to the enhancement of the surface polarity in d-CMSs. By balancing the synergistic effects of kinetics and thermodynamics, d-CMSs achieve efficient separation of C2H4/C2H6. Polymer-grade C2H4 of 99.71% purity can be achieved with 75% recovery using the devised d-CMSs as reflected in a two-bed vacuum swing adsorption simulation.

Boundary-Rich Carbon-Based Electrocatalysts with Manganese(II)-Coordinated Active Environment for Selective Synthesis of Hydrogen Peroxide.

Coordinated manganese (Mn) electrocatalysts owing to their electronic structure flexibility, non-toxic and earth abundant features are promising for electrocatalytic reactions. However, achieving selective hydrogen peroxide (H2 O2 ) production through two electron oxygen reduction (2e-ORR) is a challenge on Mn-centered catalysts. Targeting this goal, we report on the creation of a secondary Mn(II)-coordinated active environment with reactant enrichment effect on boundary-rich porous carbon-based electrocatalysts, which facilitates the selective and rapid synthesis of H2 O2 through 2e-ORR. The catalysts exhibit nearly 100 % Faradaic efficiency and H2 O2 productivity up to 15.1 mol gcat -1 h-1 at 0.1 V versus reversible hydrogen electrode, representing the record high activity for Mn-based electrocatalyst in H2 O2 electrosynthesis. Mechanistic studies reveal that the epoxide and hydroxyl groups surrounding Mn(II) centers improve spin state by modifying electronic properties and charge transfer, thus tailoring the adsorption strength of *OOH intermediate. Multiscale simulations reveal that the high-curvature boundaries facilitate oxygen (O2 ) adsorption and result in local O2 enrichment due to the enhanced interaction between carbon surface and O2 . These merits together ensure the efficient formation of H2 O2 with high local concentration, which can directly boost the tandem reaction of hydrolysis of benzonitrile to benzamide with nearly 100 % conversion rate and exclusive benzamide selectivity.

Beyond the Selectivity-Capacity Trade-Off: Ultrathin Carbon Nanoplates with Easily Accessible Ultramicropores for High-Efficiency Propylene/Propane Separation.

Rapid and highly efficient C3H6/C3H8 separation over porous carbons is seriously hindered by the trade-off effect between adsorption capacity and selectivity. Here, we report a new type of porous carbon nanoplate (CNP) featuring an ultrathin thickness of around 8 nm and easily accessible ultramicropores (approximately 5.0 Å). The ultrathin nature of the material allows a high accessibility of gas molecules into the interior transport channels, and ultramicropores magnify the difference in diffusion behavior between C3H6 and C3H8 molecules, together ensuring a remarkable C3H6/C3H8 separation performance. The CNPs show a high and steady C3H6 capacity of up to 3.03 mmol g-1 at 298 K during consecutive dynamic cycles, which is superior to that of the state-of-the-art porous carbons and even porous crystalline materials. In particular, the CNPs show a rapid gas diffusivity, which is 1000 times higher than that of conventional activated carbons. This research provides a promising design principle for addressing the selectivity-capacity trade-off for other types of adsorbent materials.

Boosting Selective Oxidation of Ethylene to Ethylene Glycol Assisted by In situ Generated H2 O2 from O2 Electroreduction.

Ethylene glycol is a useful organic compound and chemical intermediate for manufacturing various commodity chemicals of industrial importance. Nevertheless, the production of ethylene glycol in a green and safe manner is still a long-standing challenge. Here, we established an integrated, efficient pathway for oxidizing ethylene into ethylene glycol. Mesoporous carbon catalyst produces H2 O2 , and titanium silicalite-1 catalyst would subsequently oxidize ethylene into ethylene glycol with the in situ generated H2 O2 . This tandem route presents a remarkable activity, i.e., 86 % H2 O2 conversion with 99 % ethylene glycol selectivity and 51.48 mmol gecat -1 h-1 production rate at 0.4 V vs. reversible hydrogen electrode. Apart from generated H2 O2 as an oxidant, there exists ⋅OOH intermediate which could omit the step of absorbing and dissociating H2 O2 over titanium silicalite-1, showing faster reaction kinetics compared to the ex situ one. This work not only provides a new idea for yielding ethylene glycol but also demonstrates the superior of in situ generated H2 O2 in tandem route.

Ion exchange in atomically thin clays and micas.

The physical properties of clays and micas can be controlled by exchanging ions in the crystal lattice. Atomically thin materials can have superior properties in a range of membrane applications, yet the ion-exchange process itself remains largely unexplored in few-layer crystals. Here we use atomic-resolution scanning transmission electron microscopy to study the dynamics of ion exchange and reveal individual ion binding sites in atomically thin and artificially restacked clays and micas. We find that the ion diffusion coefficient for the interlayer space of atomically thin samples is up to 104 times larger than in bulk crystals and approaches its value in free water. Samples where no bulk exchange is expected display fast exchange at restacked interfaces, where the exchanged ions arrange in islands with dimensions controlled by the moiré superlattice dimensions. We attribute the fast ion diffusion to enhanced interlayer expandability resulting from weaker interlayer binding forces in both atomically thin and restacked materials. This work provides atomic scale insights into ion diffusion in highly confined spaces and suggests strategies to design exfoliated clay membranes with enhanced performance.

Construction of Confined Bifunctional 2D Material for Efficient Sulfur Resource Recovery and Hg2+ Adsorption in Desulfurization.

Substantial energy penalty of valuable sulfate recovery restricts the efficiency of wet desulfurization and increases the risk of Hg0 reemission. Although the enhanced sulfite oxidation rate with cobalt-based materials can increase the energy efficiency, inactivation and poisoning of catalyst due to the competition of reactant must be addressed. Here we obtained a superwetting two-dimensional cobalt-nitrogen-doped carbon (2D Co-N-C) nanosheet featuring confined catalysis/adsorption sites for the energy-efficient sulfite oxidation and Hg2+ adsorption. The designed structure exhibits enhanced surface polarity, availability and short reactant diffusion path, thus enabling the significant catalytic TOF value of 0.085 s-1 and simultaneous mercury removal ability of 143.26 mg·g-1. The catalyst nanosheets present regenerating stabilities to improve cost-efficiency. By deployment of the Co-N-C catalysts, a marked reduction of heat penalty up to 69% can be achieved, which makes this catalytic pathway for sulfur resource recovery economically feasible in real industry scenario.

MOF-Derived Robust and Synergetic Acid Sites Inducing C-N Bond Disruption for Energy-Efficient CO2 Desorption.

Amine-based scrubbing technique is recognized as a promising method of capturing CO2 to alleviate climate change. However, the less stability and poor acidity of solid acid catalysts (SACs) limit their potential to further improve amine regeneration activity and reduce the energy penalty. To address these challenges, here, we introduce two-dimensional (2D) cobalt-nitrogen-doped carbon nanoflakes (Co-N-C NSs) driven by a layered metal-organic framework that work as SACs. The designed 2D Co-N-C SACs can exhibit promising stability, superhydrophilic surface, and acidity. Such 2D structure also contains well-confined Co-N4 Lewis acid sites and -OH Brønsted acid sites to have a synergetic effect on C-N bond disruption and significantly increase CO2 desorption rate by 281% and reduce the reaction temperatures to 88 °C, minimizing water evaporation by 20.3% and subsequent regeneration energy penalty by 71.7% compared to the noncatalysis.

Self-Pillared Ultramicroporous Carbon Nanoplates for Selective Separation of CH4 /N2.

There is growing evidence that pillaring up a densely packed ultramicroporous two-dimensional (2D) structure is an effective strategy to reduce their internal diffusion. Reliable pillaring paradigms, however, is rather challenging. Here we report a one-pot multi-component sequential assembly method for the preparation of a new self-pillared 2D polymer and ultramicroporous carbon with integrated surface protrusions. The molecular level pillaring process is surprisingly fast, that is, in 10 min. The thickness of nanoplate edge and the density (roughness), angle as well as height of protrusions can be precisely tuned. Exemplified in coal bed methane purification/separation, this unique pillared 2D carbons exhibit a CH4 /N2 selectivity up to 24 at a low CH4 partial pressure and two orders of magnitude faster CH4 diffusion kinetics than the commercial carbon molecular sieves. This solution synthesis methodology is generalizable for creation and fine tuning of pillared 2D heterostructures.

Wiggling Mesopores Kinetically Amplify the Adsorptive Separation of Propylene/Propane.

Adsorptive separation is an appealing technology for propylene and propane separation; however, the challenge lies in the design of efficient adsorbents which can distinguish the two molecules having very similar properties. Here we report a kinetically amplified separation by creating wiggling mesopores in structurally robust carbon monoliths. The wiggling mesopores with alternating wide and narrow segments afford a surface area of 413 m2 g-1 and a tri-modal pore size distribution centered at 1.5, 4.2 and 6.6 nm, respectively. The synergistically kinetic and equilibrium effects were observed and quantitatively assessed, which together ensured a remarkable propylene/propane selectivity up to 39. This selectivity outperformed not only the available carbon adsorbents but also highly competitive among the dominated crystalline porous adsorbents. In addition, the wiggling mesoporous carbon adsorbent showed excellent dynamical separation stability, which ensured its great potential in practical molecular separations.

An Asymmetric Supercapacitor-Diode (CAPode) for Unidirectional Energy Storage.

A new asymmetric capacitor concept is proposed providing high energy storage capacity for only one charging direction. Size-selective microporous carbons (w<0.9 nm) with narrow pore size distribution are demonstrated to exclusively electrosorb small anions (BF4 - ) but size-exclude larger cations (TBA+ or TPA+ ), while the counter electrode, an ordered mesoporous carbon (w>2 nm), gives access to both ions. This architecture exclusively charges in one direction with high rectification ratios (RR=12), representing a novel capacitive analogue of semiconductor-based diodes ("CAPode"). By precise pore size control of microporous carbons (0.6 nm, 0.8 nm and 1.0 nm) combined with an ordered mesoporous counter electrode (CMK-3, 4.8 nm) electrolyte cation sieving and unidirectional charging is demonstrated by analyzing the device charge-discharge response and monitoring individual electrodes of the device via in situ NMR spectroscopy.

Unusual ultra-hydrophilic, porous carbon cuboids for atmospheric-water capture.

There is significant interest in high-performance materials that can directly and efficiently capture water vapor, particularly from air. Herein, we report a class of novel porous carbon cuboids with unusual ultra-hydrophilic properties, over which the synergistic effects between surface heterogeneity and micropore architecture is maximized, leading to the best atmospheric water-capture performance among porous carbons to date, with a water capacity of up to 9.82 mmol g(-1) at P/P0 =0.2 and 25 °C (20% relative humidity or 6000 ppm). Benefiting from properties, such as defined morphology, narrow pore size distribution, and high heterogeneity, this series of functional carbons may serve as model materials for fundamental research on carbon chemistry and the advance of new types of materials for water-vapor capture as well as other applications requiring combined highly hydrophilic surface chemistry, developed hierarchical porosity, and excellent stability.

Anomalous enhancement of humid CO2 capture by local surface bound water in polar carbon nanopores.

Removal of confined space carbon dioxide (CO2) that is in low concentration and with coexisting water is necessary but challenging by physical adsorption method. To make the removal process effective, rendering the nanopore surface hydrophobic to resist water is the popular way. Instead of preventing water from occupying the nanopores, in this work, we propose to utilize the guest water for the spatially selective formation of local surface bound water and further induce the preferential CO2 capture. We observe an anomalous enhancement of CO2 capture performance under humid conditions over carbon nanopores with spatially selective polar sites. It is evidenced that the surface bound water is formed at non-CO2-selective areas of polar carbon nanopores, thus creating additional CO2 trapping sites. This work may inspire the design of environment tolerable materials for molecular separation and purification under harsh conditions.

Revealing an Extended Adsorption/Insertion-Filling Sodium Storage Mechanism in Petroleum Coke-Derived Amorphous Carbon.

Amorphous carbon holds great promise as anode material for sodium-ion batteries due to its cost-effectiveness and good performance. However, its sodium storage mechanism, particularly the insertion process and origin of plateau capacity, remains controversial. Here, an extended adsorption/insertion-filling sodium storage mechanism is proposed using petroleum coke-derived amorphous carbon as a multi-microcrystalline model. Combining in situ X-ray diffraction, in situ Raman, theoretical calculations, and neutron scattering, the effective storage form and location of sodium ions in amorphous carbon are revealed. The sodium adsorption at defect sites leads to a high-potential sloping capacity. The sodium insertion process occurs in both the pseudo-graphite phase (d002 > 0.370 nm) and graphite-like phase (0.345 ≤ d002 < 0.370 nm) rather than the graphite phase, contributing to low-potential sloping capacity. The sodium filling into accessible closed pores forms quasi-metallic sodium clusters, contributing to plateau capacity. The threshold of the effective interlayer spacing for sodium insertion is extended to 0.345 nm, breaking the consensus of insertion interlayer threshold and enhancing understanding of closed pore filling. The extended adsorption/insertion-filling mechanism explains the sodium storage behavior of amorphous carbon with different microstructures, providing theoretical guidance for the rational design of high-performance amorphous carbon anodes.

pH-Regulated Refinement of Pore Size in Carbon Spheres for Size-Sieving of Gaseous C8 , C6 and C3 Hydrocarbon Pairs.

Selective separation of industrial important C8 , C6 and C3 hydrocarbon pairs by physisorbents can greatly reduce the energy intensity related to the currently used cryogenic distillation techniques. The achievement of size-sieving based on carbonaceous materials is desirable, but commonly hindered by the random structure of carbons often with a broad pore size distribution. Herein, a pH-regulated pre-condensation strategy was introduced to control the carbon pore architecture by the sp2 /sp3 hybridization of precursor. The lower pH value during pre-condensation of glucose facilitates the growth of aromatic nanodomains, rearrangement of stacked layers and a concomitant transition from sp3 -C to sp2 -C. The subsequent pyrolysis endows the pore size manipulated from 6.8 to 4.8 Šand narrowly distributed over a range of 0.2 Å. The refined pores enable effective size-sieving of C8 , C6 and C3 hydrocarbon pairs with high separation factor of 1.9 and 4.9 for C8 xylene (X) isomers para-X/meta-X and para-X/ortho-X, respectively, 5.1 for C6 alkane isomers n-hexane/3-methylpentane, and 22.0 for C3 H6 /C3 H8 . The excellent separation performance based-on size exclusion effect is validated by static adsorption isotherms and dynamic breakthrough experiments. This synthesis strategy provides a means of exploring advanced carbonaceous materials with controlled hybridized structure and pore sizes for challenging separation needs.

Recent Advances in Carbon-Based Adsorbents for Adsorptive Separation of Light Hydrocarbons.

Light hydrocarbons (LHs) separation is an important process in petrochemical industry. The current separation technology predominantly relies on cryogenic distillation, which results in considerable energy consumption. Adsorptive separation using porous solids has received widespread attention due to its lower energy footprint and higher efficiency. Thus, tremendous efforts have been devoted to the design and synthesis of high-performance porous solids. Among them, porous carbons display exceptional stability, tunable pore structure, and surface chemistry and thus represent a class of novel adsorbents upon achieving the matched pore structures for LHs separations. In this review, the modulation strategies toward advanced carbon-based adsorbents for LHs separation are firstly reviewed. Then, the relationships between separation performances and key structural parameters of carbon adsorbents are discussed by exemplifying specific separation cases. The research findings on the control of the pore structures as well as the quantification of the adsorption sites are highlighted. Finally, the challenges of carbonaceous adsorbents facing for LHs separation are given, which would motivate us to rationally design more efficient absorbents and separation processes in future.

Asymmetric heterojunctions between size different 2D flakes intensify the ionic diode behaviour.

Here we report on the facile formation of asymmetric heterojunctions between laterally size different 2D flakes, which leads to a prominent gradient in charge distribution at the nanocontact interface and triggers ionic diode-like transport behaviour with a rectification ratio of 110.

Temperature-programmed precise control over the sizes of carbon nanospheres based on benzoxazine chemistry.

On the basis of benzoxazine chemistry, we have established a new way to synthesize highly uniform carbon nanospheres with precisely tailored sizes and high monodispersity. Using monomers including resorcinol, formaldehyde, and 1,6-diaminohexane, and in the presence of Pluronic F127 surfactant, polymer nanospheres are first synthesized under precisely programmed reaction temperatures. Subsequently, they are pseudomorphically and uniformly converted to carbon nanospheres in high yield, due to the excellent thermal stability of such polybenzoxazine-based polymers. The correlation between the initial reaction temperature (IRT) and the nanosphere size fits well with the quadratic function model, which can in turn predict the nanosphere size at a set IRT. The nanosphere sizes can easily go down to 200 nm while retaining excellent monodispersity, i.e., polydispersity <5%. The particle size uniformity is evidenced by the formation of large areas of periodic assembly structure. NMR, FT-IR, and elemental analyses prove the formation of a polybenzoxazine framework. As a demonstration of their versatility, nanocatalysts composed of highly dispersed Pd nanoparticles in the carbon nanospheres are fabricated, which show high conversion and selectivity, great reusability, and regeneration ability, as evidenced in a selective oxidation of benzyl alcohol to benzaldehyde under moderate conditions.

Structurally designed synthesis of mechanically stable poly(benzoxazine-co-resol)-based porous carbon monoliths and their application as high-performance CO2 capture sorbents.

Porous carbon monoliths with defined multilength scale pore structures, a nitrogen-containing framework, and high mechanical strength were synthesized through a self-assembly of poly(benzoxazine-co-resol) and a carbonization process. Importantly, this synthesis can be easily scaled up to prepare carbon monoliths with identical pore structures. By controlling the reaction conditions, porous carbon monoliths exhibit fully interconnected macroporosity and mesoporosity with cubic Im3m symmetry and can withstand a press pressure of up to 15.6 MPa. The use of amines in the synthesis results in a nitrogen-containing framework of the carbon monolith, as evidenced by the cross-polarization magic-angle-spinning NMR characterization. With such designed structures, the carbon monoliths show outstanding CO(2) capture and separation capacities, high selectivity, and facile regeneration at room temperature. At ~1 bar, the equilibrium capacities of the monoliths are in the range of 3.3-4.9 mmol g(-1) at 0 °C and of 2.6-3.3 mmol g(-1) at 25 °C, while the dynamic capacities are in the range of 2.7-4.1 wt % at 25 °C using 14% (v/v) CO(2) in N(2). The carbon monoliths exhibit high selectivity for the capture of CO(2) over N(2) from a CO(2)/N(2) mixture, with a separation factor ranging from 13 to 28. Meanwhile, they undergo a facile CO(2) release in an argon stream at 25 °C, indicating a good regeneration capacity.

Nitrogen and boron doped carbon layer coated multiwall carbon nanotubes as high performance anode materials for lithium ion batteries.

Lithium ion batteries (LIBs) are at present widely used as energy storage and conversion device in our daily life. However, due to the limited power density, the application of LIBs is still restricted in some areas such as commercial vehicles or heavy-duty trucks. An effective strategy to solve this problem is to increase energy density through the development of battery materials. At the same time, a stable long cycling battery is a great demand of environmental protection and industry. Herein we present our new materials, nitrogen and boron doped carbon layer coated multiwall carbon nanotubes (NBC@MWCNTs), which can be used as anodes for LIBs. The electrochemical results demonstrate that the designed NBC@MWCNTs electrode possesses high stable capacity over an ultra-long cycling lifespan (5000 cycles) and superior rate capability even at very high current density (67.5 A g-1). Such impressive lithium storage properties could be ascribed to the synergistic coupling effect of the distinctive structural features, the reduced diffusion length of lithium ions, more active sites generated by doped atoms for lithium storage, as well as the enhancement of the electrode structural integrity. Taken together, these results indicate that the N, B-doped carbon@MWCNTs materials may have great potential for applications in next-generation high performance rechargeable batteries.