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.

Deep Potential Molecular Dynamics Study of Propane Oxidative Dehydrogenation.

Oxidative dehydrogenation (ODH) of light alkanes is a key process in the oxidative conversion of alkanes to alkenes, oxygenated hydrocarbons, and COx (x = 1,2). Understanding the underlying mechanisms extensively is crucial to keep the ODH under control for target products, e.g., alkenes rather than COx, with minimal energy consumption, e.g., during the alkene production or maximal energy release, e.g., during combustion. In this work, deep potential (DP), a neural network atomic potential developed in recent years, was employed to conduct large-scale accurate reactive dynamic simulations. The model was trained on a sufficient data set obtained at the density functional theory level. The intricate reaction network was elucidated and organized in the form of a hierarchical network to demonstrate the key features of the ODH mechanisms, including the activation of propane and oxygen, the influence of propyl reaction pathways on the propene selectivity, and the role of rapid H2O2 decomposition for sustainable and efficient ODH reactions. The results indicate the more complex reaction mechanism of propane ODH than that of ethane ODH and are expected to provide insights in the ODH catalyst optimization. In addition, this work represents the first application of deep potential in the ODH mechanistic study and demonstrates the ample advantages of DP in the study of mechanism and dynamics of complex systems.

Hydrogen Spillover-Driven Dynamic Evolution and Migration of Iron Oxide for Structure Regulation of Versatile Magnetic Nanocatalysts.

Magnetic nanocatalysts with properties of easy recovery, induced heating, or magnetic levitation play a crucial role in advancing intelligent techniques. Herein, we report a method for the synthesis of versatile core-shell-type magnetic nanocatalysts through "noncontact" hydrogen spillover-driven reduction and migration of iron oxide with the assistance of Pd. In situ analysis techniques were applied to visualize the dynamic evolution of the magnetic nanocatalysts. Pd facilitates the dissociation of hydrogen molecules into activated H*, which then spills and thus drives the iron oxide reduction, gradual outward split, and migration through the carbonaceous shell. By controlling the evolution stage, nanocatalysts having diverse architectures including core-shell, split core-shell, or hollow type, each featuring Pd or PdFe loaded on the carbon shell, can be obtained. As a showcase, a magnetic nanocatalyst (Pd-loaded split core-shell) can hydrogenate crotonaldehyde to butanal (26 624 h-1 in TOF, ∼100% selectivity), outperforming reported Pd-based catalysts. This is due to the synergy of the enhanced local magnetothermal effect and the preferential adsorption of -C═C on Pd with a small d bandwidth. Another catalyst (PdFe-loaded split core-shell) also delivers a robust performance in phenylacetylene semihydrogenation (100% conversion, 97.5% selectivity) as PdFe may inhibit the overhydrogenation of -C═C. Importantly, not only Pd, other noble metals (e.g., Pt, Ru, and Au) also showed a similar property, revealing a general rule that hydrogen spillover drives the dynamic reduction, splitting, and migration of encapsulated nanosized iron oxide, resulting in diverse structures. This study would offer a structure-controllable fabrication of high-performance magnetic nanocatalysts for various applications.

Salt-assisted surface charge driven synthesis of large pores alumina as carbon tolerance support for propane dehydrogenation.

Porous alumina has been widely used as catalytic support for industrial processes. Under carbon emission constraints, developing a low-carbon porous aluminum oxide synthesis method is a long-standing challenge for low-carbon technology. Herein, we report a method involving the only use of elements of the aluminum-containing reactants (e.g. sodium aluminate and aluminum chloride), sodium chloride was introduced as the coagulation electrolyte to adjust the precipitation process. Noticeably, the adjustment of the dosages of NaCl would allow us to tailor the textural properties and surface acidity with a volcanic-type change of the assembled alumina coiled plates. As a result, porous alumina with a specific surface area of 412 m2/g, large pore volume of 1.96 cm3/g, and concentrated pore size distribution at 30 nm was obtained. The function of salt on boehmite colloidal nanoparticles was proven by colloid model calculation, dynamic light scattering, and scanning/transmission electron microscopy. Afterward, the synthesized alumina was loaded with PtSn to prepare catalysts for the propane dehydrogenation reaction. The obtained catalysts were active but showed different deactivation behavior that was related to the coke resistance capability of the support. We figure out the correlation between pore structure and the activity of the PtSn catalysts associated with the maximum conversion of 53 % and minimum deactivation constant occurring at the pore diameter around 30 nm of the porous alumina. This work offers new insight into the synthesis of porous alumina.

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.

Nanoengineered Design of inside-Heating Hot Nanoreactor Surrounded by Cool Environment for Selective Hydrogenations.

Catalysts with designable intelligent nanostructure may potentially drive the changes in chemical reaction techniques. Herein, a multi-function integrating nanocatalyst, Pt-containing magnetic yolk-shell carbonaceous structure, having catalysis function, microenvironment heating, thermal insulation, and elevated pressure into a whole is designed, which induces selective hydrogenation within heating-constrained nanoreactors surrounded by ambient environment. As a demonstration, carbonyl of α, ß-unsaturated aldehydes/ketones are selectively hydrogenated to unsaturated alcohols with a >98% selectivity at a nearly complete conversion under mild conditions of 40 °C and 3 bar instead of harsh requirements of 120 °C and 30 bar. It is creatively demonstrated that the locally increased temperature and endogenous pressure (estimated as ≈120 °C, 9.7 bar) in the nano-sized space greatly facilitate the reaction kinetics under an alternating magnetic field. The outward-diffused products to the "cool environment" remain thermodynamically stable, avoiding the over-hydrogenation that often occurs under constantly heated conditions of 120 °C. Regulation of the electronic state of Pt by sulfur doping of carbon allows selective chemical adsorption of the CO group and consequently leads to selective hydrogenation. It is expected that such a multi-function integrated catalyst provides an ideal platform for precisely operating a variety of organic liquid-phase transformations under mild reaction conditions.

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.

Auto-accelerated dehydrogenation of alkane assisted by in-situ formed olefins over boron nitride under aerobic conditions.

Oxidative dehydrogenation (ODH) of alkane over boron nitride (BN) catalyst exhibits high olefin selectivity as well as a small ecological carbon footprint. Here we report an unusual phenomenon that the in-situ formed olefins under reactions are in turn actively accelerating parent alkane conversion over BN by interacting with hydroperoxyl and alkoxyl radicals and generating reactive species which promote oxidation of alkane and olefin formation, through feeding a mixture of alkane and olefin and DFT calculations. The isotope tracer studies reveal the cleavage of C-C bond in propylene when co-existing with propane, directly evidencing the deep-oxidation of olefins occur in the ODH reaction over BN. Furthermore, enhancing the activation of ethane by the in-situ formed olefins from propane is successfully realized at lower temperature by co-feeding alkane mixture strategy. This work unveils the realistic ODH reaction pathway over BN and provides an insight into efficiently producing olefins.

In Situ Generated Boron Peroxo as Mild Oxidant in Propane Oxidative Dehydrogenation Revealed by Density Functional Theory Study.

Boron-based materials catalyzing oxidative dehydrogenation is emerging as a promising protocol for efficient conversion of light alkanes to olefins, while the origin of its remarkable selectivity remains unclear. By means of density functional theory calculations, this work addresses the crucial role of boron peroxo as the mild oxidant in propane ODH: (1) Surface boron peroxo species can be generated in situ in the presence of peroxo species, preferably at the >B-O-B< sites of the zigzag edge, and show high activity to dehydrogenate propane (ΔG⧧ = 13.5 kcal/mol, ΔG = 8.9 kcal/mol). (2) The >B-O-O· site shows high discriminability of secondary H over primary H of the propane molecule, leading to significantly higher yield of iso-propyl (CH3CHCH3) than n-propyl (CH3CH2CH2); thus, propene formation is favored over deep oxidation. This provides physical insights into the origin of the remarkable olefin selectivity in the boron-containing ODH catalytic systems.

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.

Kinetics-controlled regulation for homogeneous nucleation and growth of colloidal polymer and carbon nanospheres.

Size regulation of uniform polymer nanospheres (PNSs) and carbon nanospheres (CNSs) below 100 nm has been difficult and is limited by multiple factors, such as ongoing nucleation, Ostwald ripening, minimization of surface energy, and high viscosity during the nucleation and growth process. In this study, a kinetics-controlled regulation is reported for the synthesis of monodispersed PNSs and corresponding CNSs with adjustable size below 100 nm. During the synthesis of PNSs, three distinct stages including surface energy control, surface tension control and viscosity control have been observed, where the concentration of block copolymer F127 (CF127) plays a vital role in affecting the nucleation rate of PNSs and tunes the diffusion rate of monomers and migration of particles during the nucleation and growth process. As a consequence, the size of monodisperse CNSs can be customized from 100 nm down to 41 nm with PDI below 5%.

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.

Precise delivery of multi-stimulus-responsive nanocarriers based on interchangeable visual guidance.

Cancer treatment is imminent, and controlled drug carriers are an important development direction for future clinical chemotherapy. Visual guidance is a feasible means to achieve precise treatment, reduce toxicity and increase drug efficacy. However, the existing visual control methods are limited by imaging time-consuming, sensitivity and side effects. In addition, the ability of the carrier to respond to environmental stimuli in vivo is another difficulty that limits its application. Here, we propose a highly stimulus-responsive GC liposome with precise tracing and sensitive feedback capabilities. It combines magnetic resonance imaging and fluorescence imaging, and addresses the need for precise visualization by alternating imaging modalities. More importantly, GC liposomes are a carrier that can accumulate stimuli. In this paper, by tracking the fragmentation process of empty GC and drug-loaded D-GC liposomes, we confirm the synergistic effect between multiple stimuli, which can result in a more efficient drug release performance. Finally, in mice models we examined the GC liposome imaging approach and the D-GC + UV group guided by this visualization exhibited the highest tumor inhibition efficiency (6.85-fold). This study highlights the advantages of alternate visualization-guided and co-stimulation treatment strategies, and provides design ideas and potential materials for efficient and less toxic cancer treatments.

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.

Sensitive and precise visually guided drug delivery nanoplatform with dual activation of pH and light.

Controlled-release drug carriers in cancer therapy are the most ideal way to reduce toxicity and improve drug efficacy. Since light stimulation is precise and operable, most multi-stimulation response carriers utilize phototherapy to enhance release efficiency. However, phototoxicity severely limits the application of phototherapy. Herein, we designed and synthesized a Cou-ONB lipid with sensitive fluorescence feedback and multi-stimulus response. COBL liposomes prepared from Cou-ONB lipids will passively aggregate at the tumor and guide phototherapy by fluorescence. More importantly, it can reflect the drug release effect in vivo through its own sensitive fluorescence changes, further enabling precise phototherapy and reducing phototoxicity. In this paper, the multi-stimulus superimposed response and precise fluorescence-guided performance of COBL liposomes were investigated at the molecular, liposome, cellular, and animal levels. Finally, tumor treatment experiments showed that the d-COBL-UV group had the best tumor suppression effect (5.3-fold). This paper highlights a real-time fluorescence-guided multi-stimulus superposition strategy and provides a design idea to precisely implement exogenous stimuli by displaying the degree of drug release, aiming to achieve less toxic and more efficient cancer therapy through timely and precise multi-stimulation. STATEMENT OF SIGNIFICANCE: Multi-stimulus responsive drug carriers have been extensively developed in the last decade. Visual guidance is an important tool to achieve precision medicine and precise control of drug release. However, the available visualization materials are more aimed at directing stimulation at the optimal moment. There is little discussion on when to stop exogenous stimulation and how to minimize the damage of stimulation to the patient. Here, we provide a Cou-ONB lipid that not only responds to multiple stimuli, but also provides sensitive feedback on its own dissociation with a fluorescent signal so that physicians can adjust exogenous stimuli in a timely manner. This paper provides insights to facilitate precision drug delivery systems, providing viable design ideas for precise, efficient, and less toxic cancer therapies.

Magnetic Resonance Imaging-Guided Multi-Stimulus-Responsive Drug Delivery Strategy for Personalized and Precise Cancer Treatment.

The emergence of nano-targeted controlled release liposomal drug carriers has provided a breakthrough in cancer therapy. However, their clinical efficacy is unsatisfactory, which is related to individualized differences in targeted drugs and poor in vivo release efficiency. In this paper, we prepared a class of personalized targeted and precisely controlled-release therapeutic drug carriers (GF liposomes) by co-assembling targeting and traceable o-nitrobenzyl ester lipids to propose a magnetic resonance imaging (MRI)-guided personalized in vivo targeted drug screening strategy and a multi-stimulus superimposed controlled-release strategy. Furthermore, by following the drug release process of drug-loaded liposomes (GF-D), it was found that these liposomes could rely on energy superposition to achieve more sensitive and efficient controlled drug release. In addition, the indispensable adjustment of liposome formulation for personalized MRI-based targeted therapy was verified by differential cellular uptake and in vivo magnetic resonance imaging. In the end, the 10.22-fold tumor suppression effect in the stimulus superposition group (GF-D-UV) indicates that the multi-stimulus cumulative response strategy and MRI-guided in vivo screening strategy can more effectively treat cancer. This contribution provides a concise and clever design idea for the future development of personalized precise and efficient clinical cancer therapies.

Understanding the Unique Antioxidation Property of Boron-Based Catalysts during Oxidative Dehydrogenation of Alkanes.

Boron-based catalysts show excellent performance in oxidative dehydrogenation (ODH) of light alkanes to alkenes with high selectivity and extremely good antioxidation properties. However, the anti-deep-oxidation mechanism remains unclear. Herein, we chose h-BN and B2O3 as representative boron-based catalysts to investigate their reactions with two important intermediates in the light alkane ODH, Et· (evolving to ethene) and EtO· (evolving to ethene or COx), to elucidate the origin of the antioxidation of alkanes. The density functional theory calculations reveal that surface boron sites could eliminate alkoxy in their vicinity, resulting in exceptional inhibition of alkane deep-oxidation. The analysis of the electronic and geometric structures of key stationary points showed that the oxophilicity of B determined the low deep-oxidation of alkanes, and the homoleptic coordination of B with all three ligating atoms being O moderately enhanced its oxophilicity. This work represents a novel conceptual advance in the mechanistic understanding of alkane ODH.

Selective Synthesis of Carbon Nanorings via Asymmetric Intramicellar Phase-Transition-Induced Tip-to-Tip Assembly.

The selective synthesis of energetically less favorable ring-shaped nanostructures by liquid phase synthetic chemistry is a huge challenge. Herein, we report a precise synthesis of carbon nanorings with a well-defined morphology and tunable thickness based on asymmetric intramicellar phase-transition-induced tip-to-tip assembly via mixing hydrophobic long-chain octadecanol and block copolymer F127. This orientational self-assembly depends on the hydrophobicity difference of the intermediate's surface, which triggers directional interactions that surpass the entropy cost of undesired connections and help assemble intermediates into defined ringlike structures. Based on a ringlike template, carbon nanorings with adjustable sizes can be attained by changing synthetic variables. More importantly, diverse units including crescentlike, podlike, and garlandlike nanostructures can also be created through controlling the kinetics of the self-assembly process. This discovery lays a solid foundation for the challenging construction of such a precise configuration on the nanoscale, which would not only promote fundamental studies but also pave the way for the development of advanced nanodevices with unique properties.