Correlation between the Carbon Nanotube Growth Rate and Byproducts in Antenna‐Type Remote Plasma Chemical Vapor Deposition Observed by Vacuum Ultraviolet Absorption Spectroscopy

For sp² or sp³ carbon material growth, it is important to investigate the precursors or intermediates just before growth. In this study, the density of ethylene (C₂H₄) outside the plasma discharge space and just before reaching the carbon nanotube (CNT) growth region is investigated by vacuum ultraviolet absorption spectroscopy for plasma discharge in an antenna‐type remote plasma chemical vapor deposition with a CH₄/H₂ system, with which the growth of very long (≈0.5 cm) CNT forests is achieved. Single‐wall CNT forests have the potential for application as electrodes in battery cells, vertical wiring for high current applications, and thermal interface materials. It is observed that the plasma discharge decomposes the CH₄ source gas and forms C₂H_x species, which reversibly reform to C₂H₄ in the plasma‐off state. In addition, the density of the formed C₂H₄ has a strong correlation to the CNT growth rate. Therefore, the C₂H₄ density is a good indicator of the density of C₂H_x species for CNT growth in the CH₄/H₂ plasma system.     

Runaway Carbon Dioxide Conversion Leads to Enhanced Uptake in a Nanohybrid Form of Porous Magnesium Borohydride

Leveraging molecular‐level controls to enhance CO₂ capture in solid‐state materials has received tremendous attention in recent years. Here, a new class of hybrid nanomaterials constructed from intrinsically porous γ‐Mg(BH₄)₂ nanocrystals and reduced graphene oxide (MBHg) is described. These nanomaterials exhibit kinetically controlled, irreversible CO₂ uptake profiles with high uptake capacities (>19.9 mmol g^?1) at low partial pressures and temperatures between 40 and 100 °C. Systematic experiments and first‐principles calculations reveal the mechanism of reaction between CO₂ and MBHg and unveil the role of chemically activated, metastable (BH₃‐HCOO)^? centers that display more thermodynamically favorable reaction and potentially faster reaction kinetics than the parent BH₄^? centers. Overall, it is demonstrated that size reduction to the nanoscale regime and the generation of reactive, metastable intermediates improve the CO₂ uptake properties in metal borohydride nanomaterials.     

Rational Design and Synthesis of Extremely Efficient Macroporous CoSe2–CNT Composite Microspheres for Hydrogen Evolution Reaction

Uniquely structured CoSe₂–carbon nanotube (CNT) composite microspheres with optimized morphology for the hydrogen‐evolution reaction (HER) are prepared by spray pyrolysis and subsequent selenization. The ultrafine CoSe₂ nanocrystals uniformly decorate the entire macroporous CNT backbone in CoSe₂–CNT composite microspheres. The macroporous CNT backbone strongly improves the electrocatalytic activity of CoSe₂ by improving the electrical conductivity and minimizing the growth of CoSe₂ nanocrystals during the synthesis process. In addition, the macroporous structure resulting from the CNT backbone improves the electrocatalytic activity of the CoSe₂–CNT microspheres by increasing the removal rate of generated H₂ and minimizing the polarization of the electrode during HER. The CoSe₂–CNT composite microspheres demonstrate excellent catalytic activity for HER in an acidic medium (10 mA cm^?2 at an overpotential of ≈174 mV). The bare CoSe₂ powders exhibit moderate HER activity, with an overpotential of 226 mV at 10 mA cm^?2. The Tafel slopes for the CoSe₂–CNT composite and bare CoSe₂ powders are 37.8 and 58.9 mV dec^?1, respectively. The CoSe₂–CNT composite microspheres have a slightly larger Tafel slope than that of commercial carbon‐supported platinum nanoparticles, which is 30.2 mV dec^–1.     

2D Transition Metal Carbides (MXenes) for Carbon Capture

Global warming caused by burning of fossil fuels is indisputably one of mankind's greatest challenges in the 21st century. To reduce the ever‐increasing CO₂ emissions released into the atmosphere, dry solid adsorbents with large surface‐to‐volume ratio such as carbonaceous materials, zeolites, and metal–organic frameworks have emerged as promising material candidates for capturing CO₂. However, challenges remain because of limited CO₂/N₂ selectivity and long‐term stability. The effective adsorption of CO₂ gas (≈12 mol kg^?1) on individual sheets of 2D transition metal carbides (referred to as MXenes) is reported here. It is shown that exposure to N₂ gas results in no adsorption, consistent with first‐principles calculations. The adsorption efficiency combined with the CO₂/N₂ selectivity, together with a chemical and thermal stability, identifies the archetype Ti₃C₂ MXene as a new material for carbon capture (CC) applications.     

Hybrid Cu0 and Cux+ as Atomic Interfaces Promote High‐Selectivity Conversion of CO2 to C2H5OH at Low Potential

The mixing of charge states of metal copper catalysts may lead to a much improved reactivity and selectivity toward multicarbon products for CO₂ reduction. Here, an electrocatalyst model composed of copper clusters supported on graphitic carbon nitride (g‐C₃N₄) is proposed; the connecting Cu atoms with g‐C₃N₄ can be oxidized to Cu^{x +} due to substantial charge transfer from Cu to N atoms, while others stay as Cu⁰. It is revealed that CO₂ can be captured and reduced into *CO on the Cu_t⁰ site, owing to its zero oxidation state. More importantly, C–C coupling reaction of two *CHO species on the Cu_t⁰–Cu_b^{x +} atomic interface can occur with a rather low kinetic barrier of 0.57 eV, leading to the formation of the final C₂ product, namely, C₂H₅OH. During the whole process, the limiting potential is just 0.68 V. These findings may open a new avenue for CO₂ reduction into high‐value fuels and chemicals.     

A Hierarchical Z‑Scheme α‐Fe2O3/g‐C3N4 Hybrid for Enhanced Photocatalytic CO2 Reduction

The challenge in the artificial photosynthesis of fossil resources from CO₂ by utilizing solar energy is to achieve stable photocatalysts with effective CO₂ adsorption capacity and high charge‐separation efficiency. A hierarchical direct Z‐scheme system consisting of urchin‐like hematite and carbon nitride provides an enhanced photocatalytic activity of reduction of CO₂ to CO, yielding a CO evolution rate of 27.2 µmol g^?1 h^?1 without cocatalyst and sacrifice reagent, which is >2.2 times higher than that produced by g‐C₃N₄ alone (10.3 µmol g^?1 h^?1). The enhanced photocatalytic activity of the Z‐scheme hybrid material can be ascribed to its unique characteristics to accelerate the reduction process, including: (i) 3D hierarchical structure of urchin‐like hematite and preferable basic sites which promotes the CO₂ adsorption, and (ii) the unique Z‐scheme feature efficiently promotes the separation of the electron–hole pairs and enhances the reducibility of electrons in the conduction band of the g‐C₃N₄. The origin of such an obvious advantage of the hierarchical Z‐scheme is not only explained based on the experimental data but also investigated by modeling CO₂ adsorption and CO adsorption on the three different atomic‐scale surfaces via density functional theory calculation. The study creates new opportunities for hierarchical hematite and other metal‐oxide‐based Z‐scheme system for solar fuel generation.     

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N4 Site

Manipulating the in‐plane defects of metal–nitrogen–carbon catalysts to regulate the electroreduction reaction of CO₂ (CO₂RR) remains a challenging task. Here, it is demonstrated that the activity of the intrinsic carbon defects can be dramatically improved through coupling with single‐atom Fe–N₄ sites. The resulting catalyst delivers a maximum CO Faradaic efficiency of 90% and a CO partial current density of 33 mA cm^?2 in 0.1 m KHCO_3. The remarkable enhancements are maintained in concentrated electrolyte, endowing a rechargeable Zn–CO₂ battery with a high CO selectivity of 86.5% at 5 mA cm^?2. Further analysis suggests that the intrinsic defect is the active sites for CO₂RR, instead of the Fe–N₄ center. Density functional theory calculations reveal that the Fe–N₄ coupled intrinsic defect exhibits a reduced energy barrier for CO₂RR and suppresses the hydrogen evolution activity. The high intrinsic activity, coupled with fast electron‐transfer capability and abundant exposed active sites, induces excellent electrocatalytic performance.     

A Long‐Cycle‐Life Lithium–CO2 Battery with Carbon Neutrality

Lithium–CO₂ batteries are attractive energy‐storage systems for fulfilling the demand of future large‐scale applications such as electric vehicles due to their high specific energy density. However, a major challenge with Li–CO₂ batteries is to attain reversible formation and decomposition of the Li₂CO₃ and carbon discharge products. A fully reversible Li–CO₂ battery is developed with overall carbon neutrality using MoS₂ nanoflakes as a cathode catalyst combined with an ionic liquid/dimethyl sulfoxide electrolyte. This combination of materials produces a multicomponent composite (Li₂CO₃/C) product. The battery shows a superior long cycle life of 500 for a fixed 500 mAh g^?1 capacity per cycle, far exceeding the best cycling stability reported in Li–CO₂ batteries. The long cycle life demonstrates that chemical transformations, making and breaking covalent C? O bonds can be used in energy‐storage systems. Theoretical calculations are used to deduce a mechanism for the reversible discharge/charge processes and explain how the carbon interface with Li₂CO₃ provides the electronic conduction needed for the oxidation of Li₂CO₃ and carbon to generate the CO₂ on charge. This achievement paves the way for the use of CO₂ in advanced energy‐storage systems.     

Preparation of carbon nanotubes by pyrolysis of dimethyl sulfide

Carbon nanotubes (CNTs) have been synthesized by cobalt-catalyzed pyrolysis of dimethyl sulfide (C₂H₆S). The influences of the experimental conditions on the morphology and microstructure of the product have been quantitatively analyzed. The synthesis temperature of 1000 °C is required for the decomposition of C₂H₆S. Both of the C₂H₆S vapor concentration and flow rate in the reaction chamber determine the quality of the product; the optimum C₂H₆S vapor concentration for CNT growth is around 3.36–5.48%. High flow rate of C₂H₆S vapor promote the formation of branched CNTs (BCNTs). The detailed growth mechanism of BCNTs has been proposed.     

Preparation of SiC ultrafine particles from SiH2Cl2 and C2H4 gas mixtures by a CO2 laser

Preparation of SiC ultrafine particles from SiH₂Cl₂-C₂H₄ mixtures by a CO₂ laser was investigated. The powders with specific surface area in the 8–150 m² g^–1 range were obtained by irradiating SiH₂Cl₂-C₂H₄ gas mixtures with a CO₂ laser at atmospheric pressure. X-ray diffraction of the products showed that silicon, SiC and free carbon were produced and the composition of the powders depended on the C₂H₄/SiH₂Cl₂ ratio. The reaction flame temperature changed from less than 1273 K to more than 3073 K with the laser power density and C₂H₄/SiH₂Cl₂ ratio. When SiH₂Cl₂ was irradiated with the CO₂ laser, the reaction temperature was less than 1273 K and silicon particles were formed. When the SiH₂Cl₂-C₂H₄ mixture was irradiated with a CO₂ laser, the reaction temperature was low (<1273 K) at low power density and low C₂H₄/SiH₂Cl₂ ratio, but it increased rapidly to around 3000 K at high laser power density and high C₂H₄/SiH₂Cl₂ ratio (>0.3). SiC was formed at both high and low reaction flame temperatures. It was considered that the rapid increase in the reaction flame temperature was caused by the initiation of exothermic reactions and the increase in laser absorption which was caused mainly by carbon particle formation. Hysteresis was observed between the reaction flame temperature and the power density of the laser beam. It was found that SiH₂Cl₂ underwent a disproportionation reaction on irradiation with the CO₂ laser, and silicon and SiC particles were formed through the various products of the disproportionation reaction. In particular, at low reaction flame temperature, the reactive species, such as SiH₄ and SiH₃Cl, produced by the disproportionation of SiH₂Cl₂ were considered to play an important role in the formation of silicon and SiC particles.     

Self‐Expansion Construction of Ultralight Carbon Nanotube Aerogels with a 3D and Hierarchical Cellular Structure

A novel and simple strategy is developed to construct ultralight and 3D pure carbon nanotube (CNT) aerogels by the spontaneous expansion of superaligned CNT films soaked in a piranha (mixed H₂SO₄ and H₂O₂) solution, followed by cryodesiccation. The macroscopic CNT aerogels have an extremely low apparent density (0.12 mg cm^?3), ultrahigh porosity (99.95%), high specific surface area (298 m² g^?1), and a hierarchical cellular structure with giant and ultrathin CNT sheets as cell walls. The pure CNT aerogels show high adsorption abilities for various kinds of solvents, and have great potential in widespread applications such as energy storage, catalysis, and bioengineering.     

Carbon nanotube growth at the tip of SiO2 nanocone

A well aligned growth of carbon nanotube (CNT) at the tip of SiO₂ nanocone using chemical vapor deposition (CVD) method is described. Fe particle at the tip of a nanocone has been observed to work as the catalyst for CNT growth. Initially, a number of self organized SiO₂ nanocones were grown via thermal annealing of MnCl₂ on Si substrate in the presence of H₂ gas. The average diameters of the tip and base of the nanocones were nearly 50 nm and 1 μm, respectively, with length up to 2.4 μm. At the tip of the nanocone a CNT was grown successfully. The CNT grows from the tip of the nanocone where Fe particles accumulate after the reduction of FeCl₃ at 950 °C. The accumulation point of Fe particles depends on the orientation of the nanocone tip inside the reaction tube during CVD process. Therefore, the alignment of nanotube at the tip of SiO₂ nanocone can be controlled by orientation of the nanocone in the reaction tube.     

Single Tungsten Atoms Supported on MOF‐Derived N‐Doped Carbon for Robust Electrochemical Hydrogen Evolution

Tungsten‐based catalysts are promising candidates to generate hydrogen effectively. In this work, a single‐W‐atom catalyst supported on metal–organic framework (MOF)‐derived N‐doped carbon (W‐SAC) for efficient electrochemical hydrogen evolution reaction (HER), with high activity and excellent stability is reported. High‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) and X‐ray absorption fine structure (XAFS) spectroscopy analysis indicate the atomic dispersion of the W species, and reveal that the W₁N₁C₃ moiety may be the favored local structure for the W species. The W‐SAC exhibits a low overpotential of 85 mV at a current density of 10 mA cm^?2 and a small Tafel slope of 53 mV dec^?1, in 0.1 m KOH solution. The HER activity of the W‐SAC is almost equal to that of commercial Pt/C. Density functional theory (DFT) calculation suggests that the unique structure of the W₁N₁C₃ moiety plays an important role in enhancing the HER performance. This work gives new insights into the investigation of efficient and practical W‐based HER catalysts.     

A Robust Molecular Porous Material for C2H2/CO2 Separation

A molecular porous material, MPM-2, comprised of cationic [Ni₂(AlF₆)(pzH)₈(H₂O)₂] and anionic [Ni₂Al₂F₁₁(pzH)₈(H₂O)₂] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C₂H₂ over CO₂ thanks to a high (ΔQ_st)_AC [Q_st (C₂H₂) − Q_st (CO₂)] of 13.7 kJ mol⁻¹ at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C₂H₂ from a 1:1 C₂H₂/CO₂ mixture at 298 K with effluent CO₂ purity of 99.995% and C₂H₂ purity of >95% after temperature-programmed desorption. C-H···F interactions between C₂H₂ molecules and F atoms of AlF₆³⁻ are found to enable high selectivity toward C₂H₂, as determined by density functional theory simulations.     

A Quasi‐Solid‐State Flexible Fiber‐Shaped Li–CO2 Battery with Low Overpotential and High Energy Efficiency

The rapid development of wearable electronics requires a revolution of power accessories regarding flexibility and energy density. The Li–CO₂ battery was recently proposed as a novel and promising candidate for next‐generation energy‐storage systems. However, the current Li–CO₂ batteries usually suffer from the difficulties of poor stability, low energy efficiency, and leakage of liquid electrolyte, and few flexible Li–CO₂ batteries for wearable electronics have been reported so far. Herein, a quasi‐solid‐state flexible fiber‐shaped Li–CO₂ battery with low overpotential and high energy efficiency, by employing ultrafine Mo₂C nanoparticles anchored on a carbon nanotube (CNT) cloth freestanding hybrid film as the cathode, is demonstrated. Due to the synergistic effects of the CNT substrate and Mo₂C catalyst, it achieves a low charge potential below 3.4 V, a high energy efficiency of ≈80%, and can be reversibly discharged and charged for 40 cycles. Experimental results and theoretical simulation show that the intermediate discharge product Li₂C₂O₄ stabilized by Mo₂C via coordinative electrons transfer should be responsible for the reduction of overpotential. The as‐fabricated quasi‐solid‐state flexible fiber‐shaped Li–CO₂ battery can also keep working normally even under various deformation conditions, giving it great potential of becoming an advanced energy accessory for wearable electronics.     

Synergistic Catalysis over Iron‐Nitrogen Sites Anchored with Cobalt Phthalocyanine for Efficient CO2 Electroreduction

Simultaneously achieving high Faradaic efficiency, current density, and stability at low overpotentials is essential for industrial applications of electrochemical CO₂ reduction reaction (CO₂RR). However, great challenges still remain in this catalytic process. Herein, a synergistic catalysis strategy is presented to improve CO₂RR performance by anchoring Fe‐N sites with cobalt phthalocyanine (denoted as CoPc©Fe‐N‐C). The potential window of CO Faradaic efficiency above 90% is significantly broadened from 0.18 V over Fe‐N‐C alone to 0.71 V over CoPc©Fe‐N‐C while the onset potential of CO₂RR over both catalysts is as low as ?0.13 V versus reversible hydrogen electrode. What is more, the maximum CO current density is increased ten times with significantly enhanced stability. Density functional theory calculations suggest that anchored cobalt phthalocyanine promotes the CO desorption and suppresses the competitive hydrogen evolution reaction over Fe‐N sites, while the *COOH formation remains almost unchanged, thus demonstrating unprecedented synergistic effect toward CO₂RR.     

Amorphous Molybdenum Sulfide/Carbon Nanotubes Hybrid Nanospheres Prepared by Ultrasonic Spray Pyrolysis for Electrocatalytic Hydrogen Evolution

Developing cost‐effective electrocatalysts with high activity and stability for hydrogen evolution reaction (HER) plays an important role in modern hydrogen economy. Amorphous molybdenum sulfide (MoS_x ) has recently emerged as one of the most promising alternatives to Pt‐based catalysts in HER, especially in acidic electrolytes. Here this study reports a simple ultrasonic spray pyrolysis method to synthesize hybrid HER catalysts composed of MoS_x firmly attached on entangled carbon nanotube nanospheres (MoS_x /CNTs). This synthetic process is fast, continuous, highly durable, and amenable to high‐volume production with high yields and exceptional quality. The MoS_x /CNTs hybrid catalyst prepared at 300 °C exhibits a low overpotential of 168 mV at the current density of 10 mA cm^?2 with a small Tafel slope of 36 mV dec^?1. Electrochemical measurements and X‐ray photoelectron spectroscopy analyses reveal that the CNT network not only promotes the charge transfer in corresponding HER process but also enhances the stability of the active sites in MoS_x . This work demonstrates that ultrasonic spray pyrolysis is a reliable and versatile approach for synthesizing amorphous MoS_x‐based HER catalysts.     

Impact of Interfacial Electron Transfer on Electrochemical CO2 Reduction on Graphitic Carbon Nitride/Doped Graphene

Effective electrocatalysts are required for the CO₂ reduction reaction (CRR), while the factors that can impact their catalytic activity are yet to be discovered. In this article, graphitic carbon nitride (g‐C₃N₄) is used to investigate the feasibility of regulating its CRR catalytic performance by interfacial electron transfer. A series of g‐C₃N₄/graphene with and without heteroatom doping (C₃N₄/XG, XG = BG, NG, OG, PG, G) is comprehensively evaluated for CRR through computational methods. Variable adsorption energetics and electronic structures are observed among different doping cases, demonstrating that a higher catalytic activity originates from more interfacial electron transfer. An activity trend is obtained to show the best catalytic performance of CRR to methane on C₃N₄/XG with an overpotential of 0.45 V (i.e., ?0.28 V vs reverse hydrogen electrode [RHE]). Such a low overpotential has never been achieved on any previously reported metallic CRR electrocatalysts, therefore indicating the availability of C₃N₄/XG for CO₂ reduction and the applicability of electron transfer modulation to improve CRR catalytic performance.     

Restricting Lattice Flexibility in Polycrystalline Metal–Organic Framework Membranes for Carbon Capture

Although polycrystalline metal‐organic framework (MOF) membranes offer several advantages over other nanoporous membranes, thus far they have not yielded good CO₂ separation performance, crucial for energy‐efficient carbon capture. ZIF‐8, one of the most popular MOFs, has a crystallographically determined pore aperture of 0.34 nm, ideal for CO₂/N₂ and CO₂/CH₄ separation; however, its flexible lattice restricts the corresponding separation selectivities to below 5. A novel postsynthetic rapid heat treatment (RHT), implemented in a few seconds at 360 °C, which drastically improves the carbon capture performance of the ZIF‐8 membranes, is reported. Lattice stiffening is confirmed by the appearance of a temperature‐activated transport, attributed to a stronger interaction of gas molecules with the pore aperture, with activation energy increasing with the molecular size (CH₄ > CO₂ > H₂). Unprecedented CO₂/CH₄, CO₂/N₂, and H₂/CH₄ selectivities exceeding 30, 30, and 175, respectively, and complete blockage of C₃H₆, are achieved. Spectroscopic and X‐ray diffraction studies confirm that while the coordination environment and crystallinity are unaffected, lattice distortion and strain are incorporated in the ZIF‐8 lattice, increasing the lattice stiffness. Overall, RHT treatment is a facile and versatile technique that can vastly improve the gas‐separation performance of the MOF membranes.