Facile synthesis of porous carbon nitride spheres with hierarchical three-dimensional mesostructures for CO<Subscript>2</Subscript> capture

Porous carbon nitride (CN) spheres with partially crystalline frameworks have been successfully synthesized via a nanocasting approach by using spherical mesoporous cellular silica foams (MCFs) as a hard template, and ethylenediamine and carbon tetrachloride as precursors. The resulting spherical CN materials have uniform diameters of ca. 4 μm, hierarchical three-dimensional (3-D) mesostructures with small and large mesopores with pore diameters centered at ca. 4.0 and 43 nm, respectively, a relatively high BET surface area of ∼550 m²/g, and a pore volume of 0.90 cm³/g. High-resolution transmission electron microscope (HRTEM) images, wide-angle X-ray diffraction (XRD) patterns, and Raman spectra demonstrate that the porous CN material has a partly graphitized structure. In addition, elemental analyses, X-ray photoelectron spectra (XPS), Fourier transform infrared spectra (FT-IR), and CO₂ temperature-programmed desorption (CO₂-TPD) show that the material has a high nitrogen content (17.8 wt%) with nitrogen-containing groups and abundant basic sites. The hierarchical porous CN spheres have excellent CO₂ capture properties with a capacity of 2.90 mmol/g at 25 °C and 0.97 mmol/g at 75 °C, superior to those of the pure carbon materials with analogous mesostructures. This can be mainly attributed to the abundant nitrogen-containing basic groups, hierarchical mesostructure, relatively high BET surface area and stable framework. Furthermore, the presence of a large number of micropores and small mesopores also enhance the CO₂ capture performance, owing to the capillary condensation effect.     

ZTIFs derived nitrogen-introduced high specific area and hierarchical porous carbon for oxygen reduction reaction

It is of great allure to construct nitrogen-doped hierarchical porous carbon to replace Pt-based catalysts for efficient ORR. Here, nitrogen-doped hierarchical porous carbon (NHPC) was prepared by carbonizing ZTIF-1 and KOH activating. The resultant NHPC4-700 catalyst exhibits a hierarchical porous structure and high specific area (2404 m² g^?1), which promoted the exposure of enough active sites as well as simultaneously enhanced the electron transfer rate, shorten the mass transfer pathway, enhanced ionic conductivity and carbon wetting. The results are capable of remarkably improving the ORR activities of carbon materials. The NHPC4-700 catalyst exhibits a great catalytic performance with onset potential at 0.90 V and limiting current density of ??6.0 mA cm^?2, which is close to commercial Pt/C electrocatalyst. Meanwhile, the NHPC4-700 catalysts had better stability and methanol resistance than that of Pt/C toward ORR. These superior electrochemical properties of the NHPC4-700 catalysts were closely related to their nitrogen-doped hierarchical porous structure and high specific area.

     

Novel porous starfish-like Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@nitrogen-doped carbon as an advanced anode for lithium-ion batteries

A Co-based metal-organic framework (Co-MOF) with a unique three-dimensional starfish-like nanostructure was successfully synthesized using a simple ultrasonic method.After subsequent carbonization and oxidation,a nanocomposite of nitrogen-doped carbon with a Co3O4 coating (Co3O4@N-C) with a porous starfish-like nanostructure was obtained.The final hybrid exhibited excellent lithium storage performance when evaluated as an anode material in a lithiumion battery.A remarkable and stable discharge capacity of 795 mAh·g-1 was maintained at 0.5 A·g-1 after 300 cycles.Excellent rate capability was also obtained.In addition,a full Co3O4@N-C/LiFePO4 battery displayed stable capacity retention of 95％ after 100 cycles.This excellent lithium storage performance is attributed to the unique porous starfish-like structure,which effectively buffers the volume expansion that occurs during Li+ insertion/deinsertion.Meanwhile,the nitrogendoped carbon coating enhances the electrical conductivity and provides a buffer layer to accommodate the volume change and accelerate the formation of a stable solid electrolyte interface layer.     

Preparation of ZnGa<Subscript>2</Subscript>S<Subscript>4</Subscript> by reacting GaI<Subscript>3</Subscript> and ZnI<Subscript>2</Subscript> with sulfur

We have carried out thermodynamic modeling of the GaI₃–S and ZnI₂–S systems by the method of equilibrium constants and calculated the chemical compositions of the condensed and vapor phases in the temperature range 200–500°C. Our experimental data demonstrate the feasibility of preparing zinc thiogallate by reacting gallium(III) iodide and zinc(II) iodide with sulfur. Synthesis was carried out at a temperature of 450°C over a period 2 h, followed by calcination of the product at 650°C in order to remove the residual iodine. The practical ZnGa₂S₄ yield was 92–94%.     

Influence of different dopant sites by lanthanum on the dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics

The effects of La³⁺ doped in calcium copper titanate (CCTO) at Ca²⁺ site and Cu²⁺ site were examined. The doped compositions, La_0.1Ca_0.85Cu₃Ti₄O₁₂ (LCCTO) ceramics and CaLa_0.1Cu_2.85Ti₄O₁₂ (CLCTO) ceramics were prepared by the solid-state method. The microstructure, dielectric properties, complex impedance and nonlinear I–V characteristics were studied. And it was found that La³⁺ doped at Ca²⁺ site achieved lower sintering temperatures than that doped at Cu²⁺ site in CCTO ceramics. The dielectric loss (tan δ) of LCCTO ceramics was about 0.05 at 40 kHz when the sample was sintered at 1080 °C. Dielectric constant (ε′) of LCCTO ceramics was about 3.2 × 10⁴ when the sample was sintered at 1100 °C, which was larger than CLCTO ceramics examined under the same process condition with sintering temperatures vary. The impedance analysis revealed that LCCTO ceramics had an influence of resistance of grain boundaries, which was stronger than that of CLCTO ceramics. Meanwhile, both LCCTO ceramics and CLCTO ceramics had a nonlinear-Ohmic property.     

Electric-field effect on crystal growth in the Li<Subscript>3</Subscript>PO<Subscript>4</Subscript>-Li<Subscript>4</Subscript>GeO<Subscript>4</Subscript>-Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-LiF system

We have studied the electric-field effect on crystallization processes in the Li₃PO₄-Li₄GeO₄-Li₂MoO₄-LiF system. In zero field, Li_3+x P_1?x Ge _x O₄ (x = 0.31) crystals were grown on the cathode under the conditions of this study. At low applied voltages (≤ 0.5 V), we obtained Li₂MoO₄, Li₂GeO₃, and Li_1.3Mo₃O₈. In the range V = 0.5–1 V, crystals of Li_3+x P_1?x Ge _x O₄ solid solutions with x = 0.17, 0.25, 0.28, 0.29, and 0.36 were obtained. An applied electric field was shown to reduce the melting temperature of the starting mixtures and the crystallization onset temperature.     

Single copper sites dispersed on hierarchically porous carbon for improving oxygen reduction reaction towards zinc-air battery

The demand for high-performance non-precious-metal electrocatalysts to replace the noble metal-based catalysts for oxygen reduction reaction(ORR)is intensively increasing.Herein,single-atomic copper sites supported on N-doped three-dimensional hierarchically porous carbon catalyst(Cu₁/NC)was prepared by coordination pyrolysis strategy.Remarkably,the Cu₁/NC-900 catalyst not only exhibits excellent ORR performance with a half-wave potential of 0.894 V(vs.RHE)in alkaline media,outperforming those of commercial Pt/C(0.851 V)and Cu nanoparticles anchored on N-doped porous carbon(CuNPs/NC-900),but also demonstrates high stability and methanol tolerance.Moreover,the Cu₁/NC-900 based Zn-air battery exhibits higher power density,rechargeability and cyclic stability than the one based on Pt/C.Both experimental and theoretical investigations demonstrated that the excellent performance of the as-obtained Cu₁/NC-900 could be attributed to the synergistic effect between copper coordinated by three N atoms active sites and the neighbouring carbon defect,resulting in elevated Cu d-band centers of Cu atoms and facilitating intermediate desorption for ORR process.This study may lead towards the development of highly efficient non-noble metal catalysts for applications in electrochemical energy conversion.     

Ultra-small Cu nanoparticles embedded in N-doped carbon arrays for electrocatalytic CO<Subscript>2</Subscript> reduction reaction in dimethylformamide

The development of heterogeneous catalysts with a well-defined micro structure to promote their activity and stability for electrocatalytic CO₂ reduction has been shown to be a promising strategy. In this work, Cu nanoparticles (～ 4 nm in diameter) embedded in N-doped carbon (Cu@NC) arrays were fabricated by thermal decomposition of copper tetracyanoquinodimethane (CuTCNQ) under N₂. Compared to polycrystalline copper electrodes, the Cu@NC arrays provide a significantly improved number of catalytically active sites. This resulted in a 0.7 V positive shift in onset potential, producing a catalytic current density an order magnitude larger at a potential of–2.7 V vs. Fc/Fc⁺ (Fc = ferrocene) in dimethylformamide (DMF). By controlling the water content in the DMF solvent, the CO₂ reduction product distribution can be tuned. Under optimal conditions (0.5 vol% water), 64% HCOO^–, 20% CO, and 13% H₂ were obtained. The Cu@NC arrays exhibited excellent catalytic stability with only a 0.5% decrease in the steady-state catalytic current during 6 h of electrolysis. The three-dimensional (3D) array structure of the Cu@NC was demonstrated to be effective for improving the catalytic activity of copper based catalysts while maintaining long-term catalytic stability.

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Facile fabrication of hierarchical BiVO<Subscript>4</Subscript>/TiO<Subscript>2</Subscript> heterostructures for enhanced photocatalytic activities under visible-light irradiation

BiVO₄/TiO₂ nanocomposites were fabricated by a facile wet-chemical process, followed by the synthesis of TiO₂ hierarchical spheres via hydrothermal method. The BiVO₄/TiO₂ nanocomposites were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV–Vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The results showed that prepared TiO₂ presented hierarchical spherical morphology self-assembled by nanoparticles and an anatase–brookite mixed crystal phase. The introduction of monoclinic BiVO₄ components retained the hierarchical structures and expanded the light response to around 510 nm. Type II BiVO₄/TiO₂ heterostructured nanocomposites exhibited improved photocatalytic degradation towards methylene blue under visible-light irradiation, especially for the composite photocatalysts with atomic Ti/Bi?=?10, which showed double degradation rate than that of pure BiVO₄. The enhanced photocatalytic mechanism of the heterostructured BiVO₄/TiO₂ nanocomposites was discussed as well.     

Enhanced photoluminescence of CoWO<Subscript>4</Subscript> in CoWO<Subscript>4</Subscript>/PbWO<Subscript>4</Subscript> nanocomposites

CoWO₄/PbWO₄ nanocomposites were successfully synthesized at room temperature (RT) by co-precipitation route without using any templates or surfactants and sintered at 600 °C for good crystallization. The sintered samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy and Zeta potential measurements. UV–Visible diffuse reflectance spectroscopy, photoluminescence (PL) and PL lifetime were studied at RT. The results indicate that the composites have two-phase composition: CoWO₄ and PbWO₄. SEM micrograph and zeta potential measurements reveal particle agglomeration. The intrinsic PL peak emission at 467 nm of CoWO₄ nano sample was enhanced upto four times by optimizing the atomic ratio of Pb/Co concentration. The interconnected interface of CoWO₄/PbWO₄ nanocomposites could have led to increase in number of recombination of electron hole pairs in CoWO₄ and enhanced its intrinsic PL emission intensity. The mechanism of enhanced PL emission for the CoWO₄/PbWO₄ nanocomposites can be attributed to charge transfer between [WO₄]^2? and [WO₆]^6? complexes due to intra particle agglomeration leading to possible interface.     

Enhanced electrochemical performance of Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>F<Subscript>3</Subscript> for Na-ion batteries with nanostructure and carbon coating

Carbon-coating Na₃V₂(PO₄)₂F₃ nanoparticles (NVPF@C NP) were prepared by a hydrothermal assisted sol–gel method and applied as cathode materials for Na-ion batteries. The as-prepared nanocomposites were composed of Na₃V₂(PO₄)₂F₃ nanoparticles with a typical size of ~?100 nm and an amorphous carbon layer with the thickness of ~?5 nm. Cyclic voltammetry, rate and cycling, and electrochemical impedance spectroscopy tests were used to discuss the effect of carbon coating and nanostructure. Results display that the as-prepared NVPF@C NP demonstrates a higher rate capability and better long cycling performance compared with bare Na₃V₂(PO₄)₂F₃ bulk (72 mA h g^?1 at 10 C vs 39 mA h g^?1 at 10 and 1 C capacity retention of 95% vs 88% after 50 cycles). The remarking electrode performance was attributed to the combination of nanostructure and carbon coating, which can provide short Na-ion diffusion distance and rapid electron migration.     

Carbon nanotube directed three-dimensional porous Li<Subscript>2</Subscript>FeSiO<Subscript>4</Subscript> composite for lithium batteries

Lithium iron silicate (Li₂FeSiO₄) is capable of affording a much higher capacity than conventional cathodes, and thus, it shows great promise for high-energy battery applications. However, its capacity has often been adversely affected by poor reaction activity due to the extremely low electronic and ionic conductivity of silicates. Here, we for the first time report on a rational engineering strategy towards a highly active Li₂FeSiO₄ by designing a carbon nanotube (CNT) directed three-dimensional (3D) porous Li₂FeSiO₄ composite. As the CNT framework enables rapid electron transport, and the rich pores allow efficient electrolyte penetration, this unique 3D Li₂FeSiO₄-CNT composite exhibits a high capacity of 214 mAh·g^?1 and retains 96% of this value over 40 cycles, thus, outstripping many previously reported Li₂FeSiO₄-based materials. Kinetic analysis reveals a high Li⁺ diffusivity due to coupling of the migration of electrons and ions. This research highlights the potential for engineering 3D porous structure to construct highly efficient electrodes for battery applications.

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Self-assembly synthesis of LaPO<Subscript>4</Subscript> hierarchical hollow spheres with enhanced photocatalytic CO<Subscript>2</Subscript>-reduction performance

Urchin-like LaPO4 hollow spheres were successfully synthesized by a facile solution route using citric acid (CA) as a structure-directing agent.The size of the three-dimensional (3D) hollow spheres was tuned by changing the concentration of CA.The formation mechanism of the 3D LaPO4 hollow spheres was revealed by studying the time-dependent morphology evolution process.Importantly,compared with monodispersed one-dimensional (1D) LaPO4 nanorods,the 3D LaPO4 hollow spheres self-assembled from nanorods showed a 6.8-fold enhancement in photocatalytic activity for CO2 reduction,which is attributed to the synergistic effect of their hierarchical hollow structure,higher light-harvesting capacity,and faster electron transfer.Our findings provide not only a simple,facile method for the synthesis of hierarchical hollow micro/nanoarchitectures but also an efficient route for enhancing the photocatalytic performance.     

Mass spectrometry of carbon nitride C<Subscript>3</Subscript>N<Subscript>4</Subscript>

Carbon nitride has been synthesized in macroscopic amounts by means of the original method based on an ecologically safe technology using inorganic initial compounds. The product has been characterized by mass spectrometry (MS), X-ray diffraction, and quantitative chemical analysis. The MS and thermochemical data show that stoichiometry of the samples of carbon nitride obtained using the proposed method corresponds to the empirical formula C₃N₄.     

Investigation for the synthesis of hierarchical Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@MnO<Subscript>2</Subscript> nanoarrays materials and their application for supercapacitor

We designed and fabricated hierarchical Co₃O₄@MnO₂ nanoarrays directly grown on nickel foam by hydrothermal and calcination methods. After the investigation of growth mechanism, we found that the deposition of MnO₂ was based on the self-decomposition of KMnO₄ and the reducibility of Co₃O₄ during the hydrothermal process. Thanks to the hierarchical structure, the obtained electrode exhibited excellent capacitive performance in supercapacitor. It delivered 21.72 F cm^?2 at a current density of 5 mA cm^?2 and retained ~94 % capacitance of initial value after 5000 cycles.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>-nanoparticle-decorated TiO<Subscript>2</Subscript> nanofiber hierarchical heterostructures with improved lithium-ion battery performance over wide temperature range

A facile strategy was designed for the fabrication of Fe₃O₄-nanoparticle-decorated TiO₂ nanofiber hierarchical heterostructures (FTHs) by combining the versatility of the electrospinning technique and the hydrothermal growth method. The hierarchical architecture of Fe₃O₄ nanoparticles decorated on TiO₂ nanofibers enables the successful integration of the binary composite into batteries to address structural stability and low capacity. In the resulting unique architecture of FTHs, the 1D heterostructures relieve the strain caused by severe volume changes of Fe₃O₄ during numerous charge-discharge cycles, and thus suppress the degradation of the electrode material. As a result, FTHs show excellent performance including higher reversible capacity, excellent cycle life, and good rate performance over a wide temperature range owing to the synergistic effect of the binary composition of TiO₂ and Fe₃O₄ and the unique features of the hierarchical nanofibers.

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An efficient Sb-SnO<Subscript>2</Subscript>-supported IrO<Subscript>2</Subscript> electrocatalyst for the oxygen evolution reaction in acidic medium

Polymer (acidic) electrolyte membrane water electrolysis suffers from insufficient catalyst activity, high cost of noble metal, and unsatisfactory durability, due to the sluggish reaction kinetics of oxygen evolution reaction and poor stability of catalysts under harsh operating environments. Aiming to enhance the utilization and durability of noble metals, a mesoporous Sb-doped SnO₂ material with high surface area and conductivity was synthesized via soft-template method to support IrO₂ catalyst. Physical characterization reveals that the as-prepared composite exhibits a rough morphology with the weak crystallinity IrO₂ upper layer covering the rutile SnO₂ crystalline phase. Electrochemical test for the IrO₂-loading-dependant activity finds that both the area-free activity and mass-specific current on the 31 wt% sample are the optimal, meaning the excellent dispersion effect coming from the mesoporous Sb-SnO₂ support and the synergy between the catalytic particles and Sb dopant. In addition, the enhancement in mass transfer efficiency and conductivity coming from the porous, IrO₂-covered cross-linked morphology and the support-active component interaction, the supported IrO₂ with 50 wt% loading marks the maximum normalized charge (227 C g^?1 IrO₂) and the highest apparent current at 1.75 V. What is more, this composite catalyst with the noble metal oxide coating is much more durable during continuous oxygen evolution procedure under a constant potential of 1.6 V because of the anchor effect from the carrier on the catalyst and a protective effect from the noble metal layer on the non-acid-tolerant support.     

Highly enhanced photocatalytic degradation of dye rhodamine B on the biogenic hierarchical porous TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> with 1D/3D-chain

A hybrid photocatalyst consisting of TiO₂ and nonporous SiO₂ (TiO₂/CS-RH) is prepared by loading TiO₂ sol on one-dimensional/three-dimensional chain (1D/3D-chain) which is synthesized from rice husk. The products are characterized by X-ray diffraction, N₂-adsorption–desorption analysis and scanning electron microscopy. Meanwhile, the corresponding photocatalytic activity is evaluated by measuring the photocatalytic oxidation of rhodamine B (RhB). The results reveal that TiO₂/CS-RH displays a hierarchical porous structure from micrometer to nanometer scale with high BET surface area (574.7–719.4 cm²/g). Meanwhile, the activity of TiO₂/CS-RH for the photocatalytic degradation of RhB in aqueous slurry is significantly higher than that of the unsupported TiO₂. The optimal TiO₂ loaded on the support was two times and then treated at 600 °C for 120 min to complete the conversion of RhB. In contrast, the unsupported TiO₂ photocatalyst could convert only 20% of RhB in the same irradiation time and condition.     

Phase modification induced drying shrinkage reduction on Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> activated slag by incorporating Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>

This paper aims to study the phase modification, reaction kinetics, mechanical properties and drying shrinkage of sodium carbonate activated slag by incorporating sodium sulfate in the activator. The results show that the reaction process is firstly controlled by CO₃ ^2? anions, and later runs similar to that of sodium sulfate activation. Besides, the relatively unstable phase gaylussite, commonly found in the sodium carbonate activation, is not observed in the reaction products upon hybrid activation, and monosulfoaluminate rather than ettringite is identified, probably caused by the reduced aluminate-to-sulfate ratio and increased pH value. The drying shrinkage is considerably reduced by up to 41% when replacing 50 wt% sodium carbonate by sodium sulfate, most possibly attributed to the induced phase modification. Furthermore, the relationships between the phase modification and drying shrinkage, and the potentially involved chemical reaction are discussed.     

A novel bioactive porous bredigite (Ca<Subscript>7</Subscript>MgSi<Subscript>4</Subscript>O<Subscript>16</Subscript>) scaffold with biomimetic apatite layer for bone tissue engineering

The aim of this study was to develop a novel bioactive, degradable and cytocompatible bredigite (Ca₇MgSi₄O₁₆) scaffold with biomimetic apatite layer for bone tissue engineering. Porous bredigite scaffolds were prepared using polymer sponge method. The bredigite scaffolds with biomimetic apatite layer (BTAP) were obtained by soaking bredigite scaffolds in simulated body fluid (SBF) for 10 days. The porosity and in vitro degradability of BTAP scaffolds were investigated. In addition, osteoblast-like cell morphology, proliferation and differentiation on BTAP scaffolds were evaluated and compared with β-tricalcium phosphate (β-TCP) scaffolds. The results showed that BTAP scaffolds possessed 90% of porosity. The degradation of BTAP scaffolds was comparable to that of β-TCP scaffolds. Cells on BTAP scaffolds spread well and presented a higher proliferation rate and differentiation level as compared with those on β-TCP scaffolds. Our results indicated that BTAP scaffolds were degradable and possessed the function to enhance cell proliferation and differentiation, and might be used as bone tissue engineering materials.