Construction,structure and photocatalysis of janus nanofiber modified by g-C3N4 nanosheets heterostructure photocatalysts

The construction of photocatalyst with gradient band structure is guided by the principle of band gap engineering. Rational structural design is advanced and applied to construct a new-typed peculiarly structural and functional carbon-based [TiO₂/C]//[Bi₂WO₆/C] Janus nanofiber modified by g-C₃N₄ nanosheets heterostructure photocatalyst (denoted as TB-JgHP). The flexible carbon-based [TiO₂/C]//[Bi₂WO₆/C] Janus nanofiber with one side responding to ultraviolet light and the other capturing visible light is fabricated by conjugate electrospinning, and then g-C₃N₄ nanosheets are uniformly grown in-situ on the surface of the Janus nanofibers by using gas-solid reaction via gasification of urea. The optimized TB-JgHP possesses remarkable hydrogen evolution efficiency (17.48 mmol h⁻¹ g⁻¹) and methylene blue degradation rate (99.2%) under simulated sunlight illumination for 100 min, demonstrating prominent dual-functional characteristics. The enhanced photocatalytic performance benefits from the unique Janus structure as well as the synergistic effects among the triple heterostructures of TiO₂ and Bi₂WO₆, g-C₃N₄ and TiO₂, g-C₃N₄ and Bi₂WO₆. The formation of gradient band structure among heterostructures is more conducive to the multi-step separation of photo-induced electron-hole pairs and more effective absorption of light. Further, flexible self-standing carbon-based photocatalysts not only have outstanding electron transport performance, but also are easy to separate from solution with preeminent recyclable stability. Based on a series of characterization techniques, it is further proved that TB-JgHP has higher carrier separation efficiency than the counterpart contrast samples. The formation mechanism of TB-JgHP is proposed, and the construction technique is established. The design philosophy and construction technique presented in this work pave a new avenue for research and development of other heterostructure photocatalysts.     

One step method of structure engineering porous graphitic carbon nitride for efficient visible-light photocatalytic reduction of Cr(Ⅵ)

Porous g-C3N4 nanosheets (PCN) were prepared by the nickel-assisted one-step thermal polymerization method.Hydrogen (H2) which was produced by the reaction between nickel (Ni) foam and ammonia (NH3) defined the structure and properties of PCN.During the formation of PCN,the participation of H2 not only enhanced the spacing between layers but also boosted the specific surface area that more active sites were exposed.Additionally,H2 promoted pores formation in the nanosheets,which was beneficial to the transfer of photons through lamellar structure and improved the absorption efficiency of visible light.Remarkably,the obtained PCN possessed better Cr(Ⅵ) photocatalytic reduction efficiency than pure g-C3N4.The reaction rate constant (k) of PCN (0.013 min-1) was approximately twice that of bare g-C3N4 (0.007 min-1).Furthermore,the effects of original pH and concentration of Cr(Ⅵ)-containing solution on removal efficiency of Cr(Ⅵ) were explored.A possible photocatalytic mechanism was proposed based on the experiments of radical scavengers and photoelectrochemical characterizations.     

Photoluminescence and hydrogen evolution properties of ZnS:Eu quantum dots

In the era of Photonics, design and development of novel rare earth ion-doped quantum dots (QDs) for optoelectronic applications has gained significant interest owing to their outstanding characteristics. Simultaneously, the creation of a new class of photocatalytic materials on the nanoscale is also imperative for environmental purification. Thus, we report on wet chemical synthesis, the structural, morphological, and optical characteristics, fluorescence, and hydrogen evolution of ZnS:Eu (0, 2, 4, and 6 at%) QDs for optoelectronic and photocatalytic applications. Comprehensive structural studies depicted that Eu³⁺ ions were efficiently substituted into the host matrix and altered the original structure of the ZnS compound. The emission spectra of the ZnS:Eu QDs exhibited distinctive red fluorescence owing to the transition of dopant ions in ⁵D₀ - ⁷F₁, ⁵D₀ - ⁷F₂, ⁵D₀ - ⁷F₃, and ⁵D₀ - ⁷F₄ energy levels of the 4f orbital of the Eu³⁺ ions. Moreover, the photocatalytic properties of ZnS:Eu (6 at%) QDs possess better catalytic efficiency toward hydrogen evolution through a water splitting mechanism under simulated sunlight irradiation. The observed photocatalytic phenomenon in the synthesized samples agreed well with the luminescence properties exhibited by the QDs.     

Techno-economic analysis of a hybrid energy system for CCHP and hydrogen production based on solar energy

A typical problem in Northeast China is that a large amount of surplus electricity has arisen owing to the serious photovoltaic power curtailment phenomenon. To effectively utilize the excess photovoltaic power, a hybrid energy system is proposed that uses surplus electricity to produce hydrogen in this paper. It combines solar energy, hydrogen production system, and Combined Cooling Heating and Power (CCHP) system to realize cooling, heating, power, and hydrogen generation. The system supplies energy for three public buildings in Dalian City, Liaoning Province, China, and the system configuration with the lowest unit energy cost (0.0615$/kWh) was obtained via optimization. Two comparison strategies were used to evaluate the hybrid energy system in terms of unit energy cost, annual total cost, fossil energy consumption, and carbon dioxide emissions. Subsequently, the annual total energy supply, typical daily loads, and cost of the optimized system were analyzed. In conclusion, the system is feasible for small area public buildings, and provides a solution to solve the phenomenon of photovoltaic power curtailment.     

Superior hydrogen evolution electrocatalysis enabled by CoP nanowire array on graphite felt

Renewable electricity-powered hydrogen production is an attractive alternative to unsustainable industrial processes, but the large-scale implantation of such sustainable technology still requires efficient and noble-metal-free electrocatalysts for driving cathodic hydrogen evolution reaction (HER), especially under alkaline conditions. In this paper, CoP nanowire array was in-situ developed on porous graphite felt (CoP/GF) as a new 3D electrocatalyst in facilitating hydrogen evolution electrocatalysis. This CoP/GF presents outstanding HER activity, requiring a low overpotential of 130 mV to deliver a current density of 20 mA cm^?2 as tested in 1.0 M KOH. Furthermore, this free-standing catalyst exhibits impressive long-term durability of up to 50 h under working conditions.     

GaN/Surface-modified graphitic carbon nitride heterojunction: Promising photocatalytic hydrogen evolution materials

The coupling of two-dimensional (2D) layered materials is an effective way to realize photocatalytic hydrogen production. Herein, using first-principles calculations, the photocatalytic properties of GaN/CNs heterojunctions formed by two different graphite-like carbon nitride materials and GaN monolayer are discussed in detail. The results show that the GaN/C₂N heterojunction can promote the effective separation of photogenerated electron and hole pairs, which is attributed to its type-II band orientation and high carrier mobility. However, the low overpotential of GaN/C₂N for photocatalytic hydrogen production limits the photocatalytic performance. On this basis, we adjust the CBM position of the GaN/C₂N heterojunction by applying an electric field to enhance its hydrogen evolution capability. In addition, the GaN/g-C₃N₄ is a type-I heterojunction, which is suitable for the field of optoelectronic devices. This work broadens the field of vision for the preparation of highly efficient photocatalysts.     

Hydrogen production by supercritical water gasification of lignin over CuO–ZnO catalyst synthesized with different methods

In this study, lignin was gasified in supercritical water with catalysis of CuO–ZnO synthesized by deposition precipitation, co-precipitation and sol-gel methods. Sol-gel synthesized CuO–ZnO showed the highest catalytic performance, and the gasification efficiency was increased by 37.92% with it. The XRD, SEM-EDS and N₂ adsorption/desorption analysis showed that the priority of the sol-gel catalyst was the smallest crystallite size, largest specific surface area and high dispersion. For sol-gel synthesized CuO–ZnO, the increase of CuO/ZnO ratio improved the gasification efficiency but reduced H₂ selectivity. And the catalytic activity was reduced with the calcination temperature above 600 °C due to enlarged crystallites and reduced pores. During sol-gel preparation, both the addition of ethanol and PEG in the solvent reduced the agglomeration and improved the catalytic activity. With CuO–ZnO prepared with 1 g PEG + water as the solvent, the highest H₂ yield of 6.86 mol/kg was obtained, which was over 1.5 times of that without catalyst.     

Responses to comments on the paper “two-dimensional Sc2C: A reversible and high capacity hydrogen storage material predicted by first-principles calculations”

A recent commentary by Santhosh and Ravindran on our paper (Int. J. Hydrogen Energy 2014, 39:10,606) demonstrated that the interaction between H₂ and MXene (Sc₂C and Ti₂C) phases are not Kubas-type and should be of weak physisorption, and thus made a conclusion that 2D Sc₂C and Ti₂C are not suitable for practical hydrogen storage applications. In this responses, we recalculated hydrogen adsorption on 2D Sc₂C and Ti₂C by using different exchange-correlation functionals. And based on the calculated results, bare MXenes (especially the Ti₂C) are suitable as hydrogen storage materials at temperatures of several tens degrees lower than room temperature. And the hydrogen adsorptions on the MXenes terminated with oxygen group were also investigated. Among the Ti₂C, Sc₂C and their oxygen-functional counterparts, the binding energy of H₂ on Sc₂CO₂ surface is the closest to the ideal range of 0.16–0.42 eV/H₂ at ambient conditions, and thus the Sc₂C with oxygen group is expected to be more suitable as hydrogen storage materials.     

Capacitive characteristics and electrosorption of hydrogen in microporous aсtivated carbon fibers

The possibility of hydrogen electrosorption in microporous activated carbons for acidic and alkaline electrolytes is shown. The electrochemical behavior of activated carbon fiber CH-900-20 has been investigated to find out the main factors, which influence the charging processes of microporous electrodes. The following methods were used: cyclic voltammetry, electrochemical impedance spectroscopy, chronoamperometry, and chronopotentiometry. A comparative analysis of the influence of the electrolyte type and electrode structure on the capacitance performances of carbon has been carried out. It is assumed that there is a potential barrier at the interface between micropores and macropores. The features of the process of hydrogen electrosorption in carbon micropores have been analyzed in detail. A possible mechanism of electrosorption in micropores that decreases the capacitance of the electric double layer with a corresponding drop of the electronic conductance of activated carbons in acidic electrolytes has been suggested. The influence of temperature on the kinetics of hydrogen electrosorption has been shown and the activation energy of this process has been estimated. An assumption has been made about the influence of the semiconductor conductivity of activated carbons on the capacitive and resistive characteristics of the electrodes.     

Operation principles for hydrogen spark ignited direct injection engines for passenger car applications

The sustainable reduction of greenhouse gas emissions from road transport requires solutions to achieve net-zero carbon dioxide emissions. Therefore, in addition to vehicles with electrified powertrains, such as those implemented in battery electric of fuel cell vehicles, internal combustion engines fueled with e-fuels or biofuels are also under discussion. An e-fuel that has come into focus recently, is hydrogen due to its potential to achieve zero tank-to-wheel and well-to-wheel carbon dioxide emissions when the electrolysis is powered by electricity from renewable sources. Due to the high laminar burning velocity, hydrogen has the potential for engine operation with high cylinder charge dilution by e.g. external exhaust gas recirculation or enleanment, resulting in increased efficiency. On the other hand, the high burning velocity and high adiabatic flame temperatures pose a challenge for engine cooling due to increased heat losses compared to conventional fuels. To further evaluate the use of hydrogen for small passenger car engines, a series production 1 L 3 cylinder gasoline engine provided by Ford Werke GmbH was modified for hydrogen direct injection. The engine was equipped with a high pressure external exhaust gas recirculation system to investigate charge dilution at stoichiometric operation. Due to limitations of the turbocharging system, very lean operation, which can achieve nitrogen oxides raw emissions below 10 ppm, was limited to part load operation below BMEP = 8 bar. Thus, a reduction of the nitrogen oxides emission level at high loads compared to stoichiometric operation was not possible. At stoichiometric operation with external exhaust gas recirculation engine efficiency can be increased significantly. The comparison of stoichiometric hydrogen and gasoline operation shows a reduced indicated efficiency with hydrogen with significant faster combustion of hydrogen at comparable centers of combustion. However, higher boost pressures would allow to achieve even higher indicated efficiencies by charge dilution compared to gasoline engine operation.