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.     

Covariance matrix adaptation evolution strategy based design of fixed structure robust H∞ loop shaping controller

This paper proposes the application of Covariance Matrix Adaptation Evolution Strategy (CMA-ES) in fixed structure H_∞ loop shaping controller design. Integral Time Absolute Error (ITAE) performance requirement is incorporated as a constraint with an objective of maximization of stability margin in the fixed structure H_∞ loop shaping controller design problem. Pneumatic servo system, separating tower process and F18 fighter aircraft system are considered as test systems. The CMA-ES designed fixed structure H_∞ loop-shaping controller is compared with the traditional H_∞ loop shaping controller, non-smooth optimization and Heuristic Kalman Algorithm (HKA) based fixed structure H_∞ loop shaping controllers in terms of stability margin. 20% perturbation in the nominal plant is used to validate the robustness of the CMA-ES designed H_∞ loop shaping controller. The effect of Finite Word Length (FWL) is considered to show the implementation difficulties of controller in digital processors. Simulation results demonstrated that CMA-ES based fixed structure H_∞ loop shaping controller is suitable for real time implementation with good robust stability and performance.     

叠合盆地凸起区多期复杂断裂特征及形成机制——以准噶尔盆地车排子凸起为例

以高精度三维地震资料为基础,结合构造演化恢复和区域构造背景,系统研究了准噶尔盆地车排子凸起断裂分布和形成机制。结果表明,车排子凸起发育深部和浅部2套断裂体系,深部断裂体系和浅部断裂体系分别发育3种断裂样式。车排子凸起共经历5个构造演化阶段,其中,晚二叠世挤压-逆冲控制了深部断裂体系的初始形成,晚侏罗世逆冲-走滑控制了深部断裂体系的最终定型,新近纪叠加掀斜、局部伸展控制了浅部断裂体系的形成。不同断裂体系在油气成藏过程中均起到了重要作用。其中:深部断裂体系的红车断裂是重要的油源断裂,低序级断层控制形成了石炭系火山岩优质储集体;浅部断裂体系使得油气向浅部层系运移调整,同时形成了断块圈闭、断鼻圈闭和断层-岩性圈闭等丰富的圈闭类型。     

The organization of biological sequences into constrained and unconstrained parts determines fundamental properties of genotype–phenotype maps

Biological information is stored in DNA, RNA and protein sequences, which can be understood as genotypes that are translated into phenotypes. The properties of genotype–phenotype (GP) maps have been studied in great detail for RNA secondary structure. These include a highly biased distribution of genotypes per phenotype, negative correlation of genotypic robustness and evolvability, positive correlation of phenotypic robustness and evolvability, shape-space covering, and a roughly logarithmic scaling of phenotypic robustness with phenotypic frequency. More recently similar properties have been discovered in other GP maps, suggesting that they may be fundamental to biological GP maps, in general, rather than specific to the RNA secondary structure map. Here we propose that the above properties arise from the fundamental organization of biological information into ‘constrained'' and ‘unconstrained'' sequences, in the broadest possible sense. As ‘constrained'' we describe sequences that affect the phenotype more immediately, and are therefore more sensitive to mutations, such as, e.g. protein-coding DNA or the stems in RNA secondary structure. ‘Unconstrained'' sequences, on the other hand, can mutate more freely without affecting the phenotype, such as, e.g. intronic or intergenic DNA or the loops in RNA secondary structure. To test our hypothesis we consider a highly simplified GP map that has genotypes with ‘coding'' and ‘non-coding'' parts. We term this the Fibonacci GP map, as it is equivalent to the Fibonacci code in information theory. Despite its simplicity the Fibonacci GP map exhibits all the above properties of much more complex and biologically realistic GP maps. These properties are therefore likely to be fundamental to many biological GP maps.     

Synthesis of double perovskite La2MnNiO6 nanoparticles as highly efficient oxygen evolution electro-catalysts

Double perovskite La₂MnNiO₆ nanoparticles (approximately 30 nm in diameter) were synthesized using a modified sol-gel method followed by a firing process and used as promising electrode materials for oxygen evolution reactions (OERs). The phase purity of the nanoparticles was verified using X-ray diffraction and Raman spectroscopy measurements. La₂MnNiO₆ nanoparticles crystallize in a monoclinic structure (P2₁/n space group) with refined lattice parameters of a = 5.461(5) Å, b = 5.512(3) Å, c = 7.760(5) Å, and β = 90.10(2)°. The elemental composition, particle size, size distribution, and surface area of the La₂MnNiO₆ nanoparticles were also investigated. La₂MnNiO₆ nanoparticles are ferromagnetic in nature and exhibit hysteresis with a saturation magnetization value of approximately 9 emu/g. La₂MnNiO₆ nanoparticles exhibit highly efficient electro-catalytic activity for OERs with a low onset over-potential (approximately 65 mV) and low Tafel slope values (120 mV/dec) in alkaline media. The over-potential of La₂MnNiO₆ nanoparticles at a current density of 10 mA/cm² is in good agreement with the reported over-potential (ƞ₁₀) of double perovskites, commercial Pt/C and IrO₂ electro-catalysts for promoting OERs.     

FeOOH–CoS composite catalyst with high catalytic performances for oxygen evolution reaction at high current density

Water electrolysis is an efficient approach for high-purity hydrogen production. However, the anodic sluggish oxygen evolution reaction (OER) always needs high overpotential and thus brings about superfluous electricity cost of water electrolysis. Therefore, exploiting highly efficient OER electrocatalysts with small overpotential especially at high current density will undoubtedly boost the development of industrial water electrolysis. Herein, we used a simple hydrothermal method to prepare a novel FeOOH–CoS nanocomposite on nickel foam (NF). The as-prepared FeOOH–CoS/NF catalyst displays an excellent OER performance with extremely low overpotentials of 306 and 329 mV at 500 and 1000 mA cm⁻² in 1.0 M KOH, respectively. In addition, the FeOOH–CoS/NF catalyst can maintain excellent catalytic stability for more than 50 h, and the OER catalytic activity shows almost no attenuation no matter after 1000 repeated CV cycles or 50 h of stability test. The high catalytic activity and stability have exceeded most non-noble metal electrocatalysts reported in literature, which makes the FeOOH–CoS/NF composite catalyst have promising applications in the industrial water electrolysis.     

基于进化算法的常减压装置模拟

提出了基于优选优生进化算法（Select—best and prepotency evolution algorithm，SPEA）的常减压装置模拟方法。以各塔的温度分布为目标，基于生产过程和分析数据，采用SPEA确定各塔板Murphree效率，从而精确描述各塔板平衡偏离程度。在实际应用中，获得具有良好精度的常减压装置模型。系统分析了SPEA算法的关键参数——优选领域大小与计算复杂性及寻优性能之间的关系，结果显示其取值为群体规模的10％最为合适。