ZnCr LDH nanosheets modified graphitic carbon nitride for enhanced photocatalytic hydrogen production

ZnCr layered double hydroxides (ZnCr LDH) nanosheets modified graphitic carbon nitride (g-C₃N₄) nanohybrids were fabricated via a self-assembly procedure through electrostatic interaction between these two components. Such 2D-2D inorganic-organic hybrid material was employed for photocatalytic hydrogen production under visible light for the first time. The physical and photophysical properties of the hybrid nanocomposites were investigated to reveal the effect of ZnCr LDH nanosheets on the photocatalytic activities of g-C₃N₄. It was found that 1 wt% ZnCr LDH nanosheets modified g-C₃N₄ was optimal for the formation of intimate interfacial contact. The visible light photocatalytic H₂ production activity over g-C₃N₄ was enhanced about 2.8 times after ZnCr LDH nanosheets modification. The significant enhancement in photocatalytic performance for ZnCr LDH/g-C₃N₄ heterojunction should be attributed to the promoted charge transfer and separation efficiency, resulting from the intimate interfacial contact and Type II band alignment between ZnCr LDH and g-C₃N₄.     

Hybrid DFT study of MWCNT/Zr-doped SrTiO3 heterostructure: Hydrogen production,electronic properties and charge Carrier mediator role of Zr4+ ion

Over the past decade, remarkable efforts have been made to design low-cost, non-toxic, stable and efficient photocatalyst for water splitting. In the present work, an effective alternative approach to enhance hydrogen production of SrTiO₃ was by coupling with MWCNT to form heterojunction followed by doping with Zr⁴⁺ ion. The observed type-II band alignment and the polarised electric field could promote the separation of photoexcited charge carriers and photocatalytic activity of these hybrid heterostructures. The theoretical calculation revealed that Zr⁴⁺ ion could act as a charge carrier mediator to transfer electrons to the SrTiO₃ surface. The MWCNT (6,12,18)/Zr-doped SrTiO₃(100) heterostructure exhibited excellent activity due to the combined effect of MWCNT (6,12,18) and Zr-doped SrTiO₃(100) monolayers compared with pure SrTiO₃. This study offers a novel understanding of designing highly active and stable SrTiO₃-based photocatalyst as efficient hydrogen generation material.     

In situ preparation of N doped orthorhombic Nb2O5 nanoplates /rGO composites for photocatalytic hydrogen generation under sunlight

The synthesis of nitrogen doped orthorhombic niobium oxide nanoplates/reduced graphene oxide composites (NNb₂O₅/rGO) and their photocatalytic activity towards hydrogen generation from water and H₂S under natural sunlight has been demonstrated, uniquely. Nanostructured NNb₂O₅/rGO is synthesized by in situ wet chemical method using urea as a source of nitrogen and optimized by varying percentage of graphene oxide (GO). X?ray diffraction (XRD) study reveals that NNb₂O₅ have orthorhombic crystal structure with crystalline size, 35 nm. Further, X?ray photoelectron spectroscopy (XPS) confirm the presence of nitrogen and rGO in NNb₂O₅/rGO nanocomposite. Morphological features of (NNb₂O₅/rGO) were examined by FE?SEM and FE?TEM showed Nb₂O₅ nanoplates of diameter 25–40 nm anchored on 2D rGO. Diffuse reflectance spectra depicts the extended absorbance in the visible region with band gap of 2.2 eV. Considering the band gap in the visible region, the photocatalytic hydrogen generation from water and H₂S has been performed. The 1 wt % rGO hybridized NNb₂O₅ (S2) exhibited superior photocatalytic hydrogen generation (537 μmol/h) from water and (1385 μmol/h) from H₂S under sunlight. The improved photocatalytic activity is attributed due to an extended absorbance in the visible region, modified electronic structure upon doping and formation of well defined NNb₂O₅/rGO interface, provides large surface area, accelerates the supression of electron and hole pairs recombination rate. In our opinion, this works may provides facile route for energy efficient and economic approach for fabrication of NNb₂O₅/rGO nanocomposites as a visible light active photocatalyst.     

Hydrogen production by steam reforming of ethanol using Ni catalysts based on ternary mixed oxides prepared by coprecipitation

Ni catalysts based on ternary mixed oxides, NiMAl (M = Mg, Ca, Zn) and NiMgN (N = La, Ce) were prepared by the coprecipitation method and characterized by N₂-sorption measurements, TGA, XRF, XRD, H₂-TPR and TEM. NiMAl (M = Mg, Ca, Zn) catalyst precursors exhibited a layered double hydroxide (LDH) structure, not observed in NiMgN (N = La, Ce) samples.     

Preparation of a novel Pd/layered double hydroxide composite membrane for hydrogen filtration and characterization by thermal cycling

A layered double hydroxide (LDH) layer was grown directly on a porous stainless steel (PSS) surface to reduce the pore opening of the PSS and to be a middle layer retarding Pd/Fe interdiffusion. A thin Pd film (∼7.85 μm) was plated on the modified PSS tube by an electroless plating method. A helium leak test proved that the thin Pd on the LDH-modified PSS substrate was free of defects. The membrane had a H₂ flux of 28–36 m³/(m² h) and H₂/He selectivity larger than 2000 at a pressure difference of 1 bar. Thermal cycling between room temperature and 673 K was performed and showed that the membrane exhibited good permeance and selectivity. Long-term evaluation (1500 h) of the membrane at 673 K showed static results of H₂ flux (∼30 m³/(m² h)) and H₂/He selectivity (∼2000) over the 1500 h test period.     

The interfacial charge transfer in triphenylphosphine-based COF/PCN heterojunctions and its promotional effects on photocatalytic hydrogen evolution

In this study, the novel triphenylphosphine-based covalent organic frameworks (P–COF-1) were firstly introduced into polymeric carbon nitride (PCN) to fabricate P–COF-1/PCN heterojunctions via intermolecular π-π interaction. The photocatalytic H₂ production rate over the 9% P–COF-1/PCN heterojunctions is ca. 12 times as much as that of pure PCN. The photoelectrochemical measurements and theoretical calculation results show that due to the well-matched band structure between P–COF-1 and PCN, the photo-generated electrons tend to migrate from P–COF-1 into the conduction band of PCN through the interface of heterostructures. In addition to the π→π1 electron transition of conjugated tri-s-triazine units in the 9% P–COF-1/PCN with band gap energy of 2.53 eV, the lone pair electrons of P transition to the π1 orbitals of P–COF-1 (n→π1) with lower band gap energy of 1.82 eV results in the effective separation of photo-generated carriers and more visible light absorption, and thus enhanced the photocatalytic hydrogen evolution.     

Mo-incorporated three-dimensional hierarchical ternary nickel-cobalt-molybdenum layer double hydroxide for high-efficiency water splitting

Flowers-like 3D hierarchical ternary NiCoMo-layered double hydroxide (NiCoMo-LDH) spheres have been fabricated in substrate-free route via a one-pot hydrothermal method and utilized as efficient electrocatalysts for the OER and HER. The well-structured 3D hierarchical flowers were composed of numerous two-dimensional nanosheets, which inherently possess considerable electrochemical active sites, thereby enhancing catalytic activity. NiMo and CoMo binary LDHs, with similar morphology, were also prepared to illustrate the efficiency of the ternary LDH. The results indicate higher electrocatalytic activity for the ternary LDH as compared to binary LDHs under alkaline conditions. The NiCoMo-LDH required an overpotential as low as 202 and 93 mV to deliver a constant anodic and cathodic current density of 10 mA cm^?2 for the OER and HER, respectively. Furthermore, the NiCoMo-LDH exhibited remarkable HER activity, affording a low overpotential of 198 mV at a current density of ?100 mA cm^?2. Moreover, it could offer a stable current density of 10 mA cm^?2 for overall water splitting at 1.62 V in 1 M KOH with long-term stability for 20 h. The double-layer capacitance (C_dl) value indicated that the NiCoMo-LDH significantly influenced interface conductivity and the electrochemical active surface area. The ternary NiCoMo-LDH electrode yielded low Tafel slope values of 54 and 51 mVdec^?1 for the OER and HER. Owing to the efficient incorporation of Ni, Co, and Mo in a layered structure, synergetic effect, and high electrochemical surface area, the NiCoMo-LDH exhibited remarkable electrocatalytic activity. Such eco-friendly ternary LDHs can be used in rechargeable metal–air batteries for industrial applications.     

Biomass-derived graphene-based nanocomposite: A facile template for decoration of ultrathin nickel–aluminum layered double hydroxide nanosheets as high-performance supercapacitors

One promising approach to design of high performance supercapacitors is based on the coupling the conductive porous carbon matrixes and the electroactive components. However, the main challenge to this goal is the maintaining the long cycling life, high power and high energy densities of the related capacitors. Herein, we reported on an electroactive composite based on biomass derived 3D graphene coupled with nickel-aluminum layer double hydroxides for manufacturing a cathode material in a supercapacitor. The electrode exhibits a remarkable specific capacitance of 1390 F g⁻¹ at 1 Ag^-1, and ultrahigh rate capability of 60% from 1 to 30 Ag^-1, as well as excellent cycling stability with a capacitance retention of 92% after 5000 cycles. Furthermore, the electrode was used as the positive electrode against a Vulcan XC-72R as the negative electrode to assemble an asymmetric supercapacitor. The asymmetric supercapacitor device exhibited a maximum energy density of 173 Wh kg⁻¹ and power density of 28.8 kW kg⁻¹ as well as excellent cycling stability of 92% after 5000 cycles. The asymmetric supercapacitor could lighted up LED lamps with different colors more than 24 min. The work showed promising performance of further application in electrochemical devices.     

Ultrathin NiZrAl layered double hydroxide nanosheets derived catalyst for enhanced CO2 methanation

It is challenging to fabricate supported Ni catalysts with more active sites to improve their low-temperature catalytic performance in CO₂ methanation. Herein, firstly, ultrathin (～4 nm) NiZrAl layered double hydroxide (LDH) nanosheets were synthesized by co-precipitation method, followed by aqueous miscible organic solvent treatment (AMOST), and applied as catalyst precursors for CO₂ methanation. After H₂ reduction, the surface area of Ni particles in NiZrAl-LDH-AMO-R was significantly higher than that of NiZrAl-LDH-R without AMOST. As a result, the NiZrAl-LDH-AMO-R showed higher catalytic activity than NiZrAl-LDH-R owing to its higher H₂ and CO₂ chemisorption capacity and lower activation energy. During the 100 h-lifetime test, NiZrAl-LDH-AMO-R maintained a steady CO₂ conversion of about 92.3%. Moreover, NiZrAl-LDH-AMO-R maintained its catalytic activity after a 600 °C-hydrothermal treatment, suggesting its high stability. In situ DRIFTS results reveal that CO₂ methanation on both NiZrAl-LDH-R and NiZrAl-LDH-AMO-R followed the HCOO1 route. Interestingly, more active sites obtained after AMOST strongly promoted the generation and decomposition of HCOO1, and thus significantly improved the activity of NiZrAl-LDH-AMO-R at low temperatures.