Hierarchical Ni-BDC coated FeOOH nanosheets: A coordination tuning synergistic electrocatalyst with enhanced activity for water oxidation

Hierarchical composites represent a class of efficient electrocatalysts for renewable energy storage and conversion technologies owing to the porous structure and additional exposure of metal sites. Herein, a Ni-based metal organic frameworks (MOFs) (marked as Ni-BDC, BDC stands for 1,4-benzenedicarboxylic acid) nanosheet is successfully fabricated on hydroxyl iron oxide (FeOOH) array with carbon fiber cloth (CFC) as substrate. Benefit from the coordination tuning synergistic effect of the distinct chemical composition and the hierarchical structure for fast mass transportation, the as-obtained FeOOH@Ni-BDC illustrates excellent catalytic ability for electrochemical water oxidation with low overpotential of 270 mV to reach 10 mA/cm² current and good durability in alkaline electrolyte. The novelty of this work lies in the modulation of electronic structure of the FeOOH with Ni-BDC through coordination effect to enhance the activity of the hierarchical composite electrocatalyst. This work is expected to guide the preparation of efficient electrocatalyst for new type alternative energy sources exploitation in near future.     

Interaction of graphene,MnOx, and Ca2+ for enhanced biomimetic, ‘bubble-free’ oxygen evolution reaction at mild pH

Water electrolysis powered by renewable electricity will likely be critical to a future hydrogen economy. However, the typical use of strongly acidic or alkaline electrolytes necessitates the use of expensive materials, while bubbles add to capital and operational costs, due to blocking of the electrode surface and the necessary use of pumps and gas-liquid separators. Here ‘bubble-free’ oxygen evolution at mild pH is carried out using an electrocatalyst that mimics photosystem II (PSII). The bubble-free electrode includes a gas-extracting Gore-Tex® membrane. Edge-functionalised graphene (EFG) is included to mimic the metal-binding local protein environment, and the tyrosine residue, in the oxygen evolving complex (OEC) of PSII, while MnO_x and Ca²⁺ are incorporated to mimic the Mn₄CaO₅ cluster. Interaction between EFG, MnO_x, and Ca²⁺ results in a significant, 130 mV fall in the overpotential required to drive electrocatalytic oxygen evolution at 10 mA cm⁻², compared to the electrode without these biomimetic components.     

Enhanced graphitic domains of unreduced graphene oxide and the interplay of hydration behaviour and catalytic activity

Previous studies indicate that the properties of graphene oxide (GO) can be significantly improved by enhancing its graphitic domain size through thermal diffusion and clustering of functional groups. Remarkably, this transition takes place below the decomposition temperature of the functional groups and thus allows fine tuning of graphitic domains without compromising with the functionality of GO. By studying the transformation of GO under mild thermal treatment, we directly observe this size enhancement of graphitic domains from originally ≤40 nm² to >200 nm² through an extensive transmission electron microscopy (TEM) study. Additionally, we confirm the integrity of the functional groups during this process by a comprehensive chemical analysis. A closer look into the process confirms the theoretical predicted relevance for the room temperature stability of GO and the development of the composition of functional groups is explained with reaction pathways from theoretical calculations. We further investigate the influence of enlarged graphitic domains on the hydration behaviour of GO and the catalytic performance of single atom catalysts supported by GO. Additionally, we show that the sheet resistance of GO is reduced by several orders of magnitude during the mild thermal annealing process.     

Microstructure and damage evolution of SiCf/PyC/SiC and SiCf/BN/SiC mini-composites: A synchrotron X-ray computed microtomography study

SiC_f/PyC/SiC and SiC_f/BN/SiC mini-composites comprising single tow SiC fibre-reinforced SiC with chemical vapor deposited PyC or BN interface layers are fabricated. The microstructure evolutions of the mini-composite samples as the oxidation temperature increases (oxidation at 1000, 1200, 1400, and 1600?°C in air for 2?h) are observed by scanning electron microscopy, energy dispersive spectrometry, and X-ray diffraction characterization methods. The damage evolution for each component of the as-fabricated SiC_f/SiC composites (SiC fibre, PyC/BN interface, SiC matrix, and mesophase) is mapped as a three-dimensional (3D) image and quantified with X-ray computed tomography. The mechanical performance of the composites is investigated via tensile tests.The results reveal that tensile failure occurs after the delamination and fibre pull-out in the SiC_f/PyC/SiC composites due to the volatilization of the PyC interface at high temperatures in the air environment. Meanwhile, the gaps between the fibres and matrix lead to rapid oxidation and crack propagation from the SiC matrix to SiC fibre, resulting in the failure of the SiC_f/PyC/SiC composites as the oxidation temperature increases to 1600?°C. On the other hand, the oxidation products of B₂O₃ molten compounds (reacted from the BN interface) fill up the fracture, cracks, and voids in the SiC matrix, providing excellent strength retention at elevated oxidation temperatures. Moreover, under the protection of B₂O₃, the SiC_f/BN/SiC mini-composites show a nearly intact microstructure of the SiC fibre, a low void growth rate from the matrix to fibre, and inhibition of new void formation and the SiO₂ grain growth from room to high temperatures. This work provides guidance for predicting the service life of SiC_f/PyC/SiC and SiC_f/BN/SiC composite materials, and is fundamental for establishing multiscale damage models on a local scale.     

某340矫直机上辊快开机构裂纹原因分析及预防措施

340管线矫直机是太原重工成熟产品,在国内占有较大市场,并出口印度、印尼、缅甸、埃及等国际市场。出口印度矫直机在质保期内出现主缸裂纹问题,为探明问题原因并杜绝类似情况发生,快开机构设计静强度分析、疲劳强度分析及生产加工过程等方面探查裂纹原因并提出几点预防措施。     

Facile synthesis of carbon self-doped g-C3N4 for enhanced photocatalytic hydrogen evolution

Graphite carbon nitride (g-C₃N₄) is an appealing metal-free photocatalyst for hydrogen evolution, but the potential has been limited by its poor visible-light absorption and unsatisfactory separation of photo-induced carriers. Herein, a facile one-pot strategy to fabricate carbon self-doped g-C₃N₄ composite through the calcination of dicyanamide and trace amounts of dimethylformamide is presented. The as-obtained carbon self-doped catalyst is investigated by X-ray photoelectron spectroscopy (XPS), confirming the substitution of carbon atoms in original sites of bridging nitrogen. We demonstrate that the as-prepared materials display remarkably improved visible-light absorption and optimized electronic structure under the premise of principally maintaining the tri-s-triazine based crystal framework and surface properties. Furthermore, the carbon doped g-C₃N₄ composite simultaneously weakens the transportation barrier of charge carriers, suppresses charge recombination and raises the separated efficiency of photoinduced holes and electrons on account of the extension of pi conjugated system. As a result, carbon self-doped g-C₃N₄ exhibits 4.3 times greater photocurrent density and 5.2 times higher hydrogen evolution rate compared with its bulk counterpart under visible light irradiation.     

A new catalyst based on a nickel(II) complex of diiminodiphosphine for hydrogen evolution and oxidation

Based on that hydrogen energy is widely used in fuel cells, we focus our interests on the design and research of new complexes that catalyze the reaction in both directions, such as hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs). A highly efficient catalyst for both hydrogen evolution and oxidation, based on a nickel(II) complex, [Ni-en-P₂](ClO₄)₂, has been designed and provided by the reaction of Ni(ClO₄)₂ with N,N′-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (en-P₂) in our group. Its structure has been determined by X-ray diffraction. [Ni-en-P₂](ClO₄)₂ can electro-catalyze hydrogen evolution both from acetic acid and a neutral buffer (pH 7.0) with a turnover frequency (TOF) of 204 and 1327 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) under an overpotential (OP) of 914.6 mV and 836.6 mV, respectively. [Ni-en-P₂](ClO₄)₂ also can electro-catalyze hydrogen oxidation with a TOF of 111.7 s⁻¹ under an OP of 330 mV. The results can be attributed to that [Ni^II-en-P₂](ClO₄)₂ has three good reversible redox waves at 1.01 (Ni^III/II), −0.79 (Ni^II/I) and −1.38 V (Ni^I/0) versus Fc^+/0, respectively. We hope these findings can afford a new method for the design of electrocatalysts for both H₂ evolution and H₂ oxidation.     

Ultrasmall rhodium nanoclusters anchored on nitrogen-doped carbon nanotubes with embedded nickel nanoparticles as magnetically recyclable catalysts for efficient ammonia-borane hydrolysis

Facile yet efficient synthesis of high-performance nanocatalysts for hydrogen evolution from ammonia-borane (AB) hydrolysis is paramount. Here, we reported a novel hybrid nanocatalyst comprised of Rh nanoclusters (1.56 nm in diameters) anchored on nitrogen (N)-doped carbon nanotubes with embedded Ni nanoparticles (Ni@NCNTs), which was fabricated through adsorption of Rh ions on Ni@NCNTs. The achieved hybrid of Rh/Ni@NCNTs displayed excellent catalytic property (Turnover frequency: 959 min⁻¹) toward AB hydrolysis, higher than many prior developed Rh-based catalysts. Note that this hybrid could be reused for at least nine runs with complete AB conversion to hydrogen. Rh nanoclusters with small size exhibiting high atom utilization and the synergetic effect between Ni and Rh are responsible for the excellent catalytic property of Rh/Ni@NCNTs toward AB hydrolysis. This work highlights the importance of utilization of magnetically recyclable Ni@NCNTs as support and synergetic component for efficient hydrolysis of AB.     

Thermo-physical properties of as deposited and aged thermal barrier coatings (TBC) for gas turbines: State-of-the art and advanced TBCs

In the perspective of fuelling the future generations of gas turbines by hydrogen rich syngas, the evaluation of the effect of a higher water vapour content into the flue gases on the TBC used, or potentially usable, is a need. For this purpose YPSZ APS TBC with two different microstructures have been exposed for 500?h at different temperatures in the range 1000?°C–1250?°C either in air and air +20% vol. H₂O. The comparison between the different testing conditions has been performed in terms of sintering kinetics and phase stability, as evaluated by thermal diffusivity measurements and Synchrotron X-Rays diffraction, respectively. Furthermore the characterisation of thermal properties of two innovative TBCs (GZO-YPSZ and YAG) potentially able to withstand the CMAS attack and erosive environments, respectively, has been carried out.No clear evidence of a different behaviour of TBC has been observed, at least in the considered aging time and temperature range.