Dysprosium doped copper oxide (Cu1-xDyxO) nanoparticles enabled bifunctional electrode for overall water splitting

The production of hydrogen, a favourable alternative to an unsustainable fossil fuel remains as a significant hurdle with the pertaining challenge in the design of proficient, highly productive and sustainable electrocatalyst for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, the dysprosium (Dy) doped copper oxide (Cu_1-xDy_xO) nanoparticles were synthesized via solution combustion technique and utilized as a non-noble metal based bi-functional electrocatalyst for overall water splitting. Due to the improved surface to volume ratio and conductivity, the optimized Cu_1-xDy_xO (x = 0.01, 0.02) electrocatalysts exhibited impressive HER and OER performance respectively in 1 M KOH delivering a current density of 10 mAcm^?2 at a potential of ?0.18 V vs RHE for HER and 1.53 V vs RHE for OER. Moreover, the Dy doped CuO electrocatalyst used as a bi-functional catalyst for overall water splitting achieved a potential of 1.56 V at a current density 10 mAcm^?2 and relatively high current density of 66 mAcm^?2 at a peak potential of 2 V. A long term stability of 24 h was achieved for a cell voltage of 2.2 V at a constant current density of 30 mAcm^?2 with only 10% of the initial current loss. This showcases the accumulative opportunity of dysprosium as a dopant in CuO nanoparticles for fabricating a highly effective and low-cost bi-functional electrocatalyst for overall water splitting.     

Vacancies and phosphorus atoms assembled in amorphous urchin-like Co3O4 for highly efficient overall water splitting

Designing highly efficient and low-cost electrocatalysts is essential for water splitting. Herein, urchin-like Co₃O₄ microspheres are firstly grown on nickel foam by a hydrothermal method, then Oxygen vacancies, phosphorus doping are effectively assembled in Co₃O₄ electrocatalysts. The introduction of oxygen vacancies and phosphorus doping will adjust the electronic structure of Co which increase the intrinsic catalytic activity and improve the adsorption energy of intermediates, simultaneously, progressively transform the crystal into randomly arranged atoms structure with short range order resulting in more active sites participate in the catalytic reaction. Moreover, the catalyst of vacancies Co₃O₄-Ov and phosphorus doping Co₃O₄–P demonstrate excellent performance in oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media, Co₃O₄-Ov sample served as anode while Co₃O₄–P as cathode to form an electrolytic cell needs only 1.58 V to reach 20 mA cm^?2 for overall water splitting.     

Adaptive actuator failure compensation for cooperative robotic manipulators with parameter uncertainties

This article develops a new framework of adaptive actuator failure compensation control for cooperative manipulator systems with parameter uncertainties in addition to actuator failures, and designs and analyzes effective actuator failure compensation schemes for such robotic systems. The new adaptive control design uses an integration of multiple individual failure compensators and direct adaptation to handle various types of uncertainties in such robotic systems. The design can also be used for concurrent actuator failure cases, to expand the capability of adaptive actuator failure compensation. With a complete proof and performance analysis, it is shown that the proposed control scheme guarantees the desired closed-loop stability and asymptotic output tracking, despite actuator failures whose patterns, time instants and values are all unknown. Simulation results of a benchmark cooperative manipulator system are presented to verify the desired control performance of the system with both typical constant and square-wave actuator failure signals.     

Mesoporous g-C3N4 decorated by Ni2P nanoparticles and CdS nanorods together for enhancing photocatalytic hydrogen evolution

Ni₂P nanoparticles and CdS nanorods were grew together on a mesoporous g-C₃N₄ through a facile in-situ solvothermal approach. Under visible light (λ > 400 nm), the as-prepared ternary PCN–CdS-5% Ni₂P composite displays a high H₂ evolution rate with 2905.86 μmol g^?1 h^?1, which is about 14, 18 and 279 times that of PCN–CdS, PCN–Ni₂P and PCN, respectively. The enhanced photocatalytic activity is mainly attributed to the improved separation efficiency of the photocarriers by the type II PCN–CdS heterojunction and the effective extraction of photogenerated electrons by Ni₂P. Meanwhile, Ni₂P acts as co-catalyst to provide the photocatalytic active site for hydrogen reduction. In addition, PCN–CdS-5% Ni₂P composite exerts good stability in 12-h cycles.     

Morphological engineering of carbon-based materials: in the quest of efficient catalysts for overall water splitting

This work attempts to optimize the catalytic activity of the carbon-based materials by engineering their morphological structure. Several flake-like quantum dots with different shapes such as triangulene, elliptical, rhomboid, and square, as well as hydrocarbons having sunflower, kekulene, and snow-like structures, are considered and their electrocatalytic activities toward the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are theoretically evaluated. The activity analysis indicates that the OER overpotentials for the examined carbon materials vary in the range between 0.56 and 1.22 V. Benefiting from the improved electronic properties due to the proper morphology, remarkable catalytic activity was achieved for the snow-like morphology affording overpotentials of 0.56 V for OER and ?0.05 V for HER. In addition to snow-like, other morphologies such as triangulene and square can effectively promote acidic hydrogen evolution via Volmer-Heyrovsky mechanism. On contrary, the high values of free energies for H₂O dissociation step reveal that, under the alkaline condition, the examined carbon materials cannot be considered as efficient HER catalysts.     

温度对混凝土力学性质影响的颗粒流模拟研究

为探索混凝土在热力耦合作用下的宏观力学性质和微裂纹的变化规律,采用PFC软件中的热模块,对5种温度下的混凝土试块进行了数值模拟分析。研究结果表明:(1)温度和峰值强度呈现负相关关系,单轴抗压强度和弹性模量随温度的变化服从幂函数关系,且温度对于强度和变形参数的影响不同,强度相较于变化参数而言,对温度更加敏感。(2)随着温度的升高,由热破裂所造成的损伤不断增加,热损伤集中在界面过渡区。随着温度的升高,混凝土的破坏模式由剪切破坏逐渐转变为劈裂破坏。(3)600℃属于临界温度,在600℃之前,宏观力学性质和微裂纹扩展均变化剧烈;超过600℃以后,宏观力学性质的劣化和微裂纹的发展均放缓。     

Interfacing perovskite strontium molybdate to molybdenum disulfide nanoplatelts for boosting HER from water

Due to low hydrogen adsorption free energy at the edges of 2D-MoS₂ layered sheets, nanostructured MoS₂ materials recently are assigned to prospective electrocatalysts for hydrogen evolution reaction (HER) from water. However, the efficiency and stability of HER onto the MoS₂ designed on the conductive substrates are poor. To significantly increase the number of active sites and achieve a long-time working stability, the design of hybrid-type electrodes is crucial. Here, we report the synthesis of a new hybrid material composed of molybdenum disulfide and molybdenum oxides heterostructured with strontium molybdate. For this, a facile one-pot hydrothermal process was developed directly onto the TiO₂ nanotube carpet substrate. The interfacing of strontium molybdate at the electrode substrate verified by X-ray photoelectron spectroscopy and Time of flight secondary ions mass spectrometry (ToF SIMS) techniques. Considerable higher catalytic activity at the surface of this hybrid film, with the onset potential of 190 mV vs RHE and a Tafel slope of 66 mV dec^?1 attaining ~80 mA cm^?2 at 0.35 V overvoltage was ascertained. Exciting HER stability in comparison with the pure synthetic MoS₂ was verified by a prolonged potential cycling from 0.05 to ?0.35 V versus RHE potential and 45 h continuous HER processing at a constant current density.     

Monolithically-integrated BiVO4/p+-n GaAs1-xPx tandem photoanodes capable of unassisted solar water splitting

Monolithically-integrated tandem photoanodes were fabricated on substrates consisting of epitaxial n-GaAs_1-xP_x (x ? 0.32) grown on n⁺-GaAs wafers. A p⁺-n junction photovoltaic (PV) cell was first formed by zinc diffusion into the n-GaAs_0.68P_0.32 from a deposited ZnO coating. After diffusion the ZnO serves as a transparent electrical contact to the resulting p⁺-GaAs_0.68P_0.32 surface layer. Transparent, conducting SnO₂:F provides chemical and mechanical protection for the ZnO and the underlying PV cell, and it electrically connects this cell to a top BiVO₄ photocatalyst layer. In some photoanodes, a WO₃ thin film was interposed between the SnO₂:F and BiVO₄. All oxide coatings were produced by ultrasonic spray pyrolysis except WO₃, which was spin coated. Unassisted (unbiased) solar water splitting was achieved, with a solar-to-hydrogen efficiency approaching 2%, without addition of any co-catalyst to the BiVO₄ surface. This work can provide insights to other researchers regarding scalable, low cost approaches for the planar monolithic integration of oxide photoanode materials with PV cells to create new tandem devices.     

Porous sunflower plate-like NiFe2O4/CoNi–S heterostructure as efficient electrocatalyst for overall water splitting

Constructing high-efficient and nonprecious electrocatalysts is of primary importance for improving the efficiency of water splitting. Herein, a novel sunflower plate-like NiFe₂O₄/CoNi–S nanosheet heterostructure was fabricated via facile hydrothermal and electrodeposition methods. The as-fabricated NiFe₂O₄/CoNi–S heterostructure array exhibits remarkable bifunctional catalytic activity and stability toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media. It presents a small overpotential of 219 mV and 149 mV for OER and HER, respectively, to produce a current density of 10 mA cm^?2. More significantly, when the obtained electrodes are used as both the cathode and anode in an electrolyzer, a voltage of 1.57 V is gained at 10 mA cm^?2, with superior stability for 72 h. Such outstanding properties are ascribed to: the 3D porous network structure, which exposes more active sites and accelerates mass transfer and gas bubble emission; the high conductivity of CoNi–S, which provides faster charge transport and thus promotes the electrocatalytic reaction of the composites; and the effective interface engineering between NiFe₂O₄ (excellent performance for OER) and CoNi–S (high activity for HER), which leads to a shorter transport pathway and thus expedites electron transfer. This work provides a new strategy for designing efficient and inexpensive electrocatalysts for water splitting.     

Efficient estimation of extreme quantiles using adaptive kriging and importance sampling

This study considers an efficient method for the estimation of quantiles associated to very small levels of probability (up to O(10⁻⁹)), where the scalar performance function J is complex (eg, output of an expensive-to-run finite element model), under a probability measure that can be recast as a multivariate standard Gaussian law using an isoprobabilistic transformation. A surrogate-based approach (Gaussian Processes) combined with adaptive experimental designs allows to iteratively increase the accuracy of the surrogate while keeping the overall number of J evaluations low. Direct use of Monte-Carlo simulation even on the surrogate model being too expensive, the key idea consists in using an importance sampling method based on an isotropic-centered Gaussian with large standard deviation permitting a cheap estimation of small quantiles based on the surrogate model. Similar to AK-MCS as presented in the work of Schöbi et al., (2016), the surrogate is adaptively refined using a parallel infill criterion of an algorithm suitable for very small failure probability estimation. Additionally, a multi-quantile selection approach is developed, allowing to further exploit high-performance computing architectures. We illustrate the performances of the proposed method on several two to eight-dimensional cases. Accurate results are obtained with less than 100 evaluations of J on the considered benchmark cases.