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.     

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。     

Systematic convergence of nonlinear stochastic estimators on the Special Orthogonal Group SO(3)

This paper introduces two novel nonlinear stochastic attitude estimators developed on the Special Orthogonal Group with the tracking error of the normalized Euclidean distance meeting predefined transient and steady‐state characteristics. The tracking error is confined to initially start within a predetermined large set such that the transient performance is guaranteed to obey dynamically reducing boundaries and decrease smoothly and asymptotically to the origin in probability from almost any initial condition. The proposed estimators produce accurate attitude estimates with remarkable convergence properties using measurements obtained from low‐cost inertial measurement units. The estimators proposed in continuous form are complemented by their discrete versions for the implementation purposes. The simulation results illustrate the effectiveness and robustness of the proposed estimators against uncertain measurements and large initialization error, whether in continuous or discrete form.     

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.