Amorphous High-Entropy Hydroxides of Tunable Wide Solar Absorption for Solar Water Evaporation

The high-entropy materials have raised much attention in recent years due to their extraordinary performances in mechanical, catalysis, energy storage fields. Herein, a new type of high-entropy hydroxides (e.g., NiFeCoMnAl(OH)_x) that are amorphous and capable of broad solar absorption is reported. A facile one-pot co-precipitation method is employed to synthesize these amorphous high-entropy hydroxides (a-HEHOs) under ambient conditions. The a-HEHOs thus obtained display widely tunable bandgap (e.g., from 2.6 to 1.1 eV) due to their high-entropy and amorphous characteristics, enabling efficient light absorbance and photothermal conversion in the solar regime. Further solar water evaporation measurements show that the a-HEHOs delivered a considerable energy conversion efficiency of 55%, comparable to black titanium oxides that are synthesized using more complex and expensive methods.     

XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp3−H Functionalization

An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved.     

Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening

In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.     

Correlating Charge-Carrier Dynamics with Efficiency in Quantum-Dot Solar Cells: Can Excitonics Lead to Highly Efficient Devices?

The photovoltaic performance of quantum-dot solar cells strongly depends on the charge-carrier relaxation and recombination processes, which need to be modulated in a favorable way to obtain maximum efficiency. Recently, significant efforts have been devoted to investigate the carrier dynamics of nanocrystal sensitizers, both in solution and deposited on TiO₂ photoanodes, with the aim to correlate the excitonics with solar-energy conversion efficiency. This Minireview summarizes some proof of the concepts that efficiency can be directly correlated to the exciton dynamics of quantum-dot solar cells. The presented findings are based on CdSeS alloy, CdSe/CdS core/shell, Au/CdSe nanohybrids, and Mn-doped CdZnSSe nanocrystals, where the favourable excitonic processes are optimized to enhance the efficiency. Future prospects and limitations are addressed as well.     

Conformational Changes and Redox Properties of Bimetallic Single Helicates of Hexapyrrole-α,ω-dicarbaldehydes

The hexapyrrole-α,ω-dicarbaldehydes 1 a and 1 b were metallated with Cu^II, Ni^II, and Pd^II to give bimetallic complexes where a pair of 3 N+O four-coordinate metal planes are helically distorted and the central 2,2′-bipyrrole subunit adopts a cis or trans conformation. X-ray crystallographic analysis of the bisCu complex revealed a closed form with a cis-2,2′-bipyrrole subunit and an open form with a trans-2,2′-bipyrrole subunit. The bisPd complexes took a closed form both in the solid state and in solution. They are regarded as single helicates of two turns and the energy barrier for the interchange between an M helix and a P helix was remarkably influenced by the bulky 3,3′-substituent of the central 2,2′-bipyrrole subunit. Although the bisNi complexes adopt a closed form in the solid state, they exist as a homohelical open C₂-symmetric form or a heterohelical open C_i-symmetric form in solution. A theoretical study suggested that the closed form of 1 a Pd was stabilized by the Pd–Pd interaction. Compound 1 a Pd was reversibly oxidized by one electron at 0.14 V versus ferrocene/ferrocenium (Fc/Fc⁺) and this oxidized species showed Vis/NIR absorption bands at λ=767 and 1408 nm.     

椭球粒子声辐射力计算及分析

针对水下椭球粒子,以声散射理论为基础,采用分波序列的方法,建立了椭球粒子声辐射力的理论计算模型。进而根据声辐射力计算公式,以刚性椭球粒子和液体椭球粒子为例,计算并分析不同Bessel波束作用下椭球粒子的轴向声辐射力函数特征。数值仿真计算结果表明,对于刚性椭球粒子,扁平椭球粒子相对于细长椭球粒子更有助于激发负声辐射力；对于液体椭球粒子,细长椭球粒子相对于扁平椭球粒子更加容易产生负声辐射力；对于不同介质的椭球粒子,不同的入射波束激发的负声辐射力的效果也存在明显的差异。该结果为复杂的尺寸和介质粒子声操控技术提供了理论的可行性。     

Stochastic sensitivity analysis of coupled acoustic-structural systems under non-stationary random excitations

This paper presents a new sensitivity analysis method for coupled acoustic–structural systems subjected to non-stationary random excitations. The integral of the response power spectrum density (PSD) of the coupled system is taken as the objective function. The thickness of each structural element is used as a design variable. A time-domain algorithm integrating the pseudo excitation method (PEM), direct differentiation method (DDM) and high precision direct (HPD) integration method is proposed for the sensitivity analysis of the objective function with respect to design variables. Firstly, the PEM is adopted to transform the sensitivity analysis under non-stationary random excitations into the sensitivity analysis under pseudo transient excitations. Then, the sensitivity analysis equation of the coupled system under pseudo transient excitations is derived based on the DDM. Moreover, the HPD integration method is used to efficiently solve the sensitivity analysis equation under pseudo transient excitations in a reduced-order modal space. Numerical examples are presented to demonstrate the validity of the proposed method.     

Impurity-related optical response in a 2D and 3D quantum dot with Gaussian confinement under intense laser field

ABSTRACT

Using the two-dimensional (2D) diagonalisation method, the impurity-related electronic states and optical response in a 2D quantum dot with Gaussian confinement potential under nonresonant intense laser field are investigated. The effects of a hydrogenic impurity on the energy spectrum and binding energy of the electron and also intersubband optical absorption are calculated. The obtained numerical results show that the degeneracies of the excited electron states are broken and the absorption spectrum exhibits a redshift with the values of the laser field. The findings indicate a new degree of freedom to tune the performance of novel optoelectronic devices, based on the quantum dots and to control their specific properties by means of intense laser field and hydrogenic donor impurity. Using the same Gaussian confinement model, the electronic properties of a confined electron in the region of a spherical quantum dot are studied under the combined effects of on-centre donor impurity and a linearly polarised intense laser radiation. The three-dimensional problem is used to theoretically model, with very good agreement, some experimental findings reported in the literature related to the photoluminescence peak energy transition.