Interfacial interactions and properties of cellular structured polyurethane nanocomposite based on carbonaceous nano-fillers

In this article, we have studied the effect of carbonaceous nanofillers viz. fullerenol (0D), carboxylated multi-wall carbon nanotube (MWCNT, 1D), hydroxylated graphene (2D) and combination of carboxylated CNT and hydroxylated graphene as 3D in thermoplastic polyurethane on the tensile properties of the fabricated cellular structures. The concentration of nano-fillers was varied as 0.1, 1, and 5 wt%. Tensile properties of the nanocomposite cellular structures were measured as per ASTM D882 at 20°C (below glass transition temperature, T_g) and 40°C (above T_g). The results have shown that the tensile strength was found to increase by 200%–300% and the tensile modulus was found to increase by 150%–300% for 2D and 3D nano-fillers while significantly poor results were observed for 0D. However, the test data tensile strength and modulus showed marginal increase at 20°C and marginally low at 40°C for 1D filler. The interfacial adhesion was calculated by using experimental tensile data and the predictive models. The interfacial adhesion parameter (B_σ) calculated using Pukanszky equation was found significantly higher value for 2D (B_σ20 = 195.8) and 3D (B_σ20 = 192.0) fillers while poor adhesion was observed for 0D (B_σ20 = −81.6) fillers. The developed cellular structured materials were also evaluated by attenuated total reflection Fourier transform IR spectra, differential scanning calorimetry, X-ray diffraction, scanning electron microscope, and transmission electron microscope.     

微藻碳减排与生物质利用技术研究进展

微藻是能进行光合作用的单细胞或细胞聚集体生物，能够高效地吸收CO₂并固定在微藻生物质中，有望在CO₂减排中发挥重要作用。介绍了微藻通过光合作用固定CO₂的机理，综述了影响微藻固定CO₂效率的因素以及微藻生物质的主要利用途径，分析了微藻生物技术固定CO₂实现生物质利用的经济性，为实现“碳达峰”与“碳中和”提供新的思路与方案。     

Near-Field Drives Long-Lived Shallow Trapping of Polymeric C3N4 for Efficient Photocatalytic Hydrogen Evolution

Undesired photoelectronic dormancy through active species decay is adverse to photoactivity enhancement. An insufficient extrinsic driving force leads to ultrafast deep charge trapping and photoactive species depopulation in carbon nitride (g-C₃N₄). Excitation of shallow trapping in g-C₃N₄ with long-lived excited states opens up the possibility of pursuing high-efficiency photocatalysis. Herein, a near-field-assisted model is constructed consisting of an In₂O₃-cube/g-C₃N₄ heterojunction associated with ultrafast photodynamic coupling. This In₂O₃-cube-induced near-field assistance system provides catalytic “hot areas”, efficiently enhances the lifetimes of excited states and shallow trapping in g-C₃N₄ and this favors an increased active species density. Optical simulations combined with time-resolved transient absorption spectroscopy shows there is a built-in charge transfer and the active species lifetimes are longer in the In₂O₃-cube/g-C₃N₄ hybrid. Besides these properties, the estimated overpotential and interfacial kinetics of the In₂O₃-cube/g-C₃N₄ hybrid co-promotes the liquid phase reaction and also helps in boosting the photocatalytic performance. The photocatalytic results exhibit a tremendous improvement (34-fold) for visible-light-driven hydrogen production. Near-field-assisted long-lived active species and the influences of trap states is a novel finding for enhancing (g-C₃N₄)-based photocatalytic performance.     

Carbon corrosion mechanism on nitrogen-doped carbon support — A density functional theory study

In this work, density functional theory (DFT) calculations were used to investigate the mechanism of carbon corrosion on nitrogen-doped carbon support. Free energy diagrams were generated based on three proposed reaction pathways to evaluate corrosion mechanisms. The most energetically preferred mechanism on nitrogen-doped carbon was determined. The results show that the step of water dissociation to form ^#OH was the rate-determining step for gra-G-1N (graphene doped with graphitic N) and pyrr-G-1N (graphene doped with pyrrolic N). As for graphene doped with pyridinic N, the step of C^#OC^#O formation was critical. It was found that the control of nitrogen concentration was necessary for precisely designing optimized carbon materials. Abundance of nitrogen moieties aggravated the carbon corrosion. When the high potential was applied, specific types of graphitic N and pyridinic N were found to be favorable carbon modifications to improve carbon corrosion resistance. Moreover, the solvent effect was also investigated. The results provide theoretical insights and design guidelines to improve corrosion resistance in carbon support through material modification by inhibiting the adsorption of surface oxides (OH, O, and OOH).     

Adsorptive removal of methylene blue from aqueous solution on activated carbon prepared from Malawian baobab fruit shell wastes: Equilibrium,kinetics and thermodynamic studies

Baobab fruit shell (BFS), a renewable bio-waste from Malawian baobab tree was used as a precursor for the production of a low-cost activated carbon to remove methylene blue (MB) from aqueous solution. Parameters such as contact time, initial methylene blue concentration, adsorbent dose and temperature were studied. The adsorption process can be well described by both Langmuir isotherm and the pseudo-second-order kinetics. The maximum monolayer adsorption capacity of MB dye was ca. 334.45 mg/g. The negative value of the Gibb’s free energy and positive value of adsorption enthalpy showed the spontaneous nature and endothermic nature of the adsorption process, respectively.     

Porous nitrogen-enriched hollow carbon nanofibers as freestanding electrode for enhanced lithium storage

One-dimensional porous carbons bearing high surface areas and sufficient heteroatom doped functional-ities are essential for advanced electrochemical energy storage devices, especially for developing free-standing film electrodes. Here we develop a porous, nitrogen-enriched, freestanding hollow carbon nanofiber (PN-FHCF) electrode material via filtration of polypyrrole (PPy) hollow nanofibers formed by in situ self-degraded template-assisted strategy, followed by NH3-assisted carbonization. The PN-FHCF retains the freestanding film morphology that is composed of three-dimensional networks from the entanglement of 1D nanofiber and delivers 3.7-fold increase in specific surface area (592 m2·g-1) com-pared to the carbon without NH3 treatment (FHCF). In spite of the enhanced specific surface area, PN-FHCF still exhibits comparable high content of surface N functionalities (8.8％, atom fraction) to FHCF. Such developed hierarchical porous structure without sacrificing N doping functionalities together enables the achievement of high capacity, high-rate property and good cycling stability when applied as self-supporting anode in lithium-ion batteries, superior to those of FHCF without NH3 treatment.     

Pure and complex nanostructures using poly[bis(triiso‐propylsilylethynyl) benzodithiophene‐bis(decyltetradecyl‐thien) naphthobisthiadiazole], carbon nanotubes and reduced graphene oxide for high‐performance polymer solar cells

Crystallization of poly[bis(triiso‐propylsilylethynyl) benzodithiophene‐bis(decyltetradecyl‐thien) naphthobisthiadiazole] (PBDT‐TIPS‐DTNT‐DT) was investigated in supramolecules based on carbon nanotubes (CNTs) and reduced graphene oxide (rGO) and their grafted derivatives. The principal peaks of PBDT‐TIPS‐DTNT‐DT crystals were in the range 3.50°–3.75°. By grafting the surface of the carbonic materials, the assembling of polymer chains decreased because of hindrance of poly(3‐dodecylthiophene) (PDDT) grafts against π‐stacking. The diameters of CNT/polymer and CNT‐g‐PDDT/polymer supramolecules were 160 and 100 nm. The rGO/polymer supramolecules had the highest melting point (T_m = 282 °C) and fusion enthalpy (ΔH_m = 25.98 J g^?1), reflecting the largest crystallites and the most ordered constituents. Nano‐hybrids based on grafted rGO (276 °C and 28.26 J g^?1), CNT (275 °C and 27.32 J g^?1) and grafted CNT (268 °C and 22.17 J g^?1) were also analyzed. T_m and ΔH_m values were significantly less in corresponding melt‐grown systems. The nanostructures were incorporated in active layers of PBDT‐TIPS‐DTNT‐DT:phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) solar cells to improve the photovoltaic features. The best results were detected for PBDT‐TIPS‐DTNT‐DT:PC₇₁BM:rGO/polymer systems having J_sc = 13.11 mA cm^?2, fill factor 60% and V_oc = 0.71 V with an efficacy of 5.58%. On grafting the rGO and CNT, efficiency reductions were 12.01% (5.58%–4.91%) and 9.34% (4.07%–3.69%), respectively. © 2019 Society of Chemical Industry     

Efficient overall water splitting over a Mo(IV)-doped Co3O4/NC electrocatalyst

To meet the demand of producing hydrogen at low cost, a molybdenum (Mo)-doped cobalt oxide (Co₃O₄) supported on nitrogen (N)-doped carbon (x%Mo–Co₃O₄/NC, where x% represents Mo/Co molar ratio) is developed as an efficient bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). This defect engineering strategy is realized by a facile urea oxidation method in nitrogen atmosphere. Through X-ray diffraction (XRD) refinement and other detailed characterizations, molybdenum ion (Mo⁴⁺) is found to be doped into Co₃O₄ by substituting cobalt ion (Co²⁺) at tetrahedron site, while N is doped into carbon matrix simultaneously. 4%Mo–Co₃O₄/NC is the optimized sample to show the lowest overpotentials of 91 and 276 mV to deliver 10 mA cm^?2 for HER and OER in 1 M potassium hydroxide solution (KOH), respectively. The overall water splitting cell 4%Mo–Co₃O₄/NC||4%Mo–Co₃O₄/NC displays a voltage of 1.62 V to deliver 10 mA cm^?2 in 1 M KOH. The Mo⁴⁺ dopant modulates the electronic structure of active cobalt ion (Co³⁺) and boosts the water dissociation process during HER, while the increased amount of lattice oxygen and formation of pyridinic nitrogen due to Mo doping benefits the OER activity. Besides, the smaller grain size owing to Mo doping leads to higher electrochemically active surface area (ECSA) on 4%Mo–Co₃O₄/NC, resulting in its superior bifunctional catalytic activity.