Ammonia Oxidation Enhanced by Photopotential Generated by Plasmonic Excitation of a Bimetallic Electrocatalyst

We study how visible light influences the activity of an electrocatalyst composed of Au and Pt nanoparticles. The bimetallic composition imparts a dual functionality: the Pt component catalyzes the electrochemical oxidation of ammonia to liberate hydrogen and the Au component absorbs visible light by the excitation of localized surface plasmon resonances. Under visible-light excitation, this catalyst exhibits enhanced electrochemical ammonia oxidation kinetics, outperforming previously reported electrochemical schemes. We trace the enhancement to a photochemical potential resulting from electron–hole carriers generated in the electrocatalyst by plasmonic excitation. The photopotential responsible for enhanced kinetics scales linearly with the light intensity—a general design principle for eliciting superlative photoelectrochemical performance from catalysts comprised of plasmonic metals or hybrids. We also determine a photochemical conversion coefficient.     

MOF Encapsulated AuPt Bimetallic Nanoparticles for Improved Plasmonic-induced Photothermal Catalysis of CO2 Hydrogenation

Exploring new catalytic strategies for achieving efficient CO₂ hydrogenation under mild conditions is of great significance for environmental remediation. Herein, a composite photocatalyst Zr-based MOF encapsulated plasmonic AuPt alloy nanoparticles (AuPt@UiO-66-NH₂) was successfully constructed for the efficient photothermal catalysis of CO₂ hydrogenation. Under light irradiation at 150 °C, AuPt@UiO-66-NH₂ achieved a CO production rate of 1451 μmol g_metal⁻¹ h⁻¹ with 91 % selectivity, which far exceeded those obtained by Au@Pt@UiO-66-NH₂ with Pt shell on Au (599 μmol g_metal⁻¹ h⁻¹) and Au@UiO-66-NH₂ (218 μmol g_metal⁻¹ h⁻¹). The outstanding performances of AuPt@UiO-66-NH₂ were attributed to the synergetic effect originating from the plasmonic metal Au, doped active metal Pt, and encapsulation structure of UiO-66-NH₂ shell. This work provides a new way for photothermal catalysis of CO₂ and a reference for the design of high-performance plasmonic catalysts.     

Strength of Intramolecular Hydrogen Bonds

The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.     

Exact and exclusive electron localization indices within QTAIM atomic basins

Novel measures of electron (de)localization within the Quantum Theory of Atoms in Molecules (QTAIM) atomic basins are presented which, unlike orthodox localization indices (LIs), are fully exclusive and can be easily visualized. This work shows that QTAIM‐defined LIs describe a portion of interatomic delocalized electrons; hence, the chemical/physical interpretation of orthodox LIs is misleading. Using the recently introduced Fragment, Atomic, Localized, Delocalized, and Interatomic (FALDI) density decomposition technique we derive two novel sets of LIs and delocalization indices (DIs), by accounting for the overlap between localized and delocalized density functions. The FALDI‐based LIs and DIs perfectly recover chemically expected core and bonded electron count. Usefulness of new (de)localization indices and their 3D representations were demonstrated on a number of examples, including formamide and benzene. We therefore expect that the scheme reported in this work will provide a valuable stepping stone between classical conceptual chemistry and quantum chemical topology. © 2018 Wiley Periodicals, Inc.     

Efficiency of numerical basis sets for predicting the binding energies of hydrogen bonded complexes: evidence of small basis set superposition error compared to Gaussian basis sets

Binding energies of selected hydrogen bonded complexes have been calculated within the framework of density functional theory (DFT) method to discuss the efficiency of numerical basis sets implemented in the DFT code DMol3 in comparison with Gaussian basis sets. The corrections of basis set superposition error (BSSE) are evaluated by means of counterpoise method. Two kinds of different numerical basis sets in size are examined; the size of the one is comparable to Gaussian double zeta plus polarization function basis set (DNP), and that of the other is comparable to triple zeta plus double polarization functions basis set (TNDP). We have confirmed that the magnitudes of BSSE in these numerical basis sets are comparative to or smaller than those in Gaussian basis sets whose sizes are much larger than the corresponding numerical basis sets; the BSSE corrections in DNP are less than those in the Gaussian 6-311+G(3df,2pd) basis set, and those in TNDP are comparable to those in the substantially large scale Gaussian basis set aug-cc-pVTZ. The differences in counterpoise corrected binding energies between calculated using DNP and calculated using aug-cc-pVTZ are less than 9 kJ/mol for all of the complexes studied in the present work. The present results have shown that the cost effectiveness in the numerical basis sets in DMol3 is superior to that in Gaussian basis sets in terms of accuracy per computational cost.     

Experimental research on the localized electrochemical micro-machining

Due to several advantages and wider range of applications, micro-ECM is considered to be one of the most effective advanced future micromachining techniques. An experimental set-up for micro-ECM is constructed, which consists of various components and sub-systems, e.g. mechanical machining unit, nanosecond pulse power supply, circulation system of electrolyte, movement control component and process monitoring component. In addition, this system has the functions of fabricating micro tool electrode and machining status detection. Using the self-developed experimental system, the micro tool-electrode and the micro holes are sequentially machined. Upon the application of ultrashort voltage pulses, micro hole with 20μm diameter is obtained. Experimental results show the potential capability of electrochemical micromachining for better machining accuracy and smaller machining size. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 8, pp. 998–1003. The text was submitted by the authors in English.     

边界层流中当地感受性过程的数值研究

边界层流中当地感受性问题的研究对层流向湍流转捩过程的预测与控制起着非常关键的作用,尤其是对边界层内诱导产生三维Tollmien-Schlichting(T-S)波成因过程的探讨具有更加重要的理论意义.采用高精度、高分辨率变间距的紧致有限差分方法,直接数值模拟了在自由来流湍流与二维壁面局部粗糙相互作用下边界层内的当地感受性问题.数值计算发现,在自由来流湍流与二维壁面局部粗糙作用下,边界层内诱导形成的当地感受性过程是真实存在的;且被激发的一组三维T-S波波包沿流向发展的过程中流向涡结构将逐渐形成,其强度将越演越烈.数值结果还显示,边界层内被诱导产生当地感受性过程的波长转换机制仅使流向波数发生改变,而展向波数保持不变;以及自由来流湍流运动方向的改变将决定三维T-S波波包的传播方向,但其传播速度的大小都近似为无穷远来流速度的1/3.另外,还建立了自由来流湍流的强度和运动方向以及二维壁面局部粗糙的长度和高度与边界层内的当地感受性问题之间的关系等.这一课题的深入研究,将在进一步理解和认识层流向湍流转捩的理论机制,以及湍流的形成机理等方面均起到十分重要的作用.     

液晶染料填充阶梯型Double-period结构局域模的光学特性

利用传输矩阵法研究了液晶染料填充一维阶梯型Double-period第四代准周期结构局域模的光学特性。计算了增益前局域模与外加电场方向和正入射波方向间夹角θ的变化关系,分析了增益系数与局域模透射率的关系以及局域模在空间位置的光场分布,讨论了增益后的局域模透射率与光场强度的关系。结果表明:随着夹角θ的增大,光子禁带变宽并且只向短波方向拓展;随着夹角θ的增大,增益前的局域模向短波方向移动,透射率逐渐增大,且局域模波长的调控量为23.7nm。随着增益系数的增大,透射率先增大后减小。光场分布呈现局域现象,当夹角θ=43.4°,波长λ=595.0nm时,光强达到6个数量级。增益后的局域模透射率与光场强度呈正比关系。