具有丰富晶界的铜催化剂在气-液平衡扩散电极上高效电还原CO_(2)制C_(2)H_(4)

电催化二氧化碳还原反应(CO_(2)RR)可以将二氧化碳转化为具有高经济价值的碳氢化合物,被认为是实现碳中和并缓解能源危机的一种有潜力的技术.铜(Cu)作为一种最有应用前景的非贵金属催化剂之一,表现出较高的催化CO_(2)RR转化为多碳产物(C_(2+))的活性.然而,电催化CO_(2)还原成C_(2+)产物涉及一个动力学过程缓慢的C-C偶联反应,这导致C_(2+)产物的选择性较低,电流密度低,阻碍了其在工业电解槽中的实际应用.同时,CO_(2)RR产物的选择性不仅取决于热力学速率决定步骤,还取决于传质控制动力学.CO_(2)RR发生在固-气-液三相反应界面,气-液的平衡扩散可以有效抑制析氢竞争反应,进而提高CO_(2)RR的反应效率.本文设计合成了一种富晶界的Cu纳米带催化剂,并构建了气-液平衡扩散的电极结构,用于高效电催化二氧化碳还原制备乙烯(C_(2)H_(4)).以一种碱式碳酸铜(Cu_(2)CO_(3)(OH)_(2))纳米带为前驱体,在原位电化学还原条件下,前驱体中的Cu2+离子获得电子被还原为金属Cu,而释放的CO_(3)2-和OH-混合阴离子调节金属Cu的生长.生成的Cu纳米带由细小的纳米颗粒堆积而成,并暴露出大量的由Cu(111),Cu(200)和Cu(220)晶面形成的富晶界结构(GBs).同时,在CO_(2)RR测试中发现催化剂层的厚度是影响CO_(2)和电解质传质的关键因素.通过调整催化层厚度,CO_(2)和电解质可以同时到达催化剂表面,参与到CO_(2)RR中,实现了气-液平衡扩散,有效抑制了氢析出副反应.在晶界效应和气-液平衡扩散的协同作用下,优化后的电极在电流密度为700 mA cm^(-2)时,对C_(2)H_(4)和C_(2+).产物的法拉第效率分别高达67.2%和82.1%.此外,C_(2)H_(4)的部分电流密度可高达505 mA cm^(-2),高于大多数文献报道的结果.原位拉曼光谱和衰减全内反射表面增强红外吸收光谱结果表明,丰富的晶;界结构增强了CO_(2)在催化剂表面的活化,显著促进了*CO中间体的形成和吸附,加速了C-C偶联过程形成*OCCO和*OCCOH中间体,提高了C_(2)H_(4)和其他C_(2+)产物的产率.综上,本文设计了一种高活性Cu催化剂和电极结构,为高效电催化CO_(2)还原为C_(2)H_(4)等C_(2+)产物提供参考.

Cu-Zn-based alloy/oxide interfaces for enhanced electroreduction of CO_(2) to C_(2+) products

The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high current densities is still a challenge.Herein,we develop a Cu-Zn alloy/Cu-Zn aluminate oxide composite electrocatalytic system for enhanced conversion of CO_(2)to C_(2+)products.The Cu-Zn-Al-Layered Double Hydroxide(LDH) is used as a precursor to decompose into uniform Cu-Zn oxide/Cu-Zn aluminate pre-catalyst.Under electrochemical reduction,Cu-Zn oxide generates Cu-Zn alloy while Cu-Zn aluminate oxide remains unchanged.The alloy and oxide are closely stacked and arranged alternately,and the aluminate oxide induces the strong electron interaction of Cu,Zn and Al,creating a large number of highly active reaction interfaces composed of 0 to+3 valence metal sites.With the help of the interface effect,the optimized Cu_(9)Zn_(1)/Cu_(0.8)Zn_(0.2)Al_(2)O_(4)catalyst achieves a Faradaic efficiency of 88.5% for C_(2+)products at a current density of 400 mA cm^(-2)at-1.15 V versus reversible hydrogen electrode.The in-situ Raman and attenuate total reflectance-infrared absorption spectroscopy(ATR-IRAS) spectra show that the aluminate oxide at the interface significantly enhances the adsorption and activation of CO_(2)and the dissociation of H2O and strengthens the adsorption of CO intermediates,and the alloy promotes the C-C coupling to produce C_(2+)products.This work provides an efficient strategy to construct highly active reaction interfaces for industrial-scale electrochemical CO_(2)RR.

在有机化学实验中设置计算化学模块

计算化学快速发展,对于化学研究有非常强的指导作用,因此将其引入本科低年级实验教学很有必要。本文在调研国内外高校计算化学课程开设情况的基础上,根据本院学生特点和课程的需要,在面向大一本科生的核心实验课程——有机化学实验中引入了计算模块。模块设计从实验问题出发,将计算项目和实验紧密结合,采用分层次教学的模式进行。利用Canvas线上教学平台对微课、讲义、作业、测验等学习资源进行有效组织,通过直播课和微信群进行讨论和答疑,以翻转课堂的形式进行混合式教学,取得了很好的教学效果。

(E)-Nerolidol is a volatile signal that induces defenses against insects and pathogens in tea plants

Plants release large amounts of volatile organic compounds(VOCs)in response to attackers.Several VOCs can serve as volatile signals to elicit defense responses in undamaged tissues and neighboring plants,but many questions about the ecological functions of VOCs remain unanswered.Tea plants are impacted by two harmful invaders,the piercing herbivore Empoasca(Matsumurasca)onukii Matsuda and the pathogen Colletotrichum fructicola.To determine the VOC signals in tea,we confirmed CsOPR3 as a marker gene and set up a rapid screening method based on a 1.51 kb CsOPR3 promoter fused with aβ-glucuronidase(GUS)reporter construct(OPR3p::GUS)in Arabidopsis.Using this screening system,a terpenoid volatile(E)-nerolidol was identified as a potent signal that elicits plant defenses.The early responses triggered by(E)-nerolidol included the activation of a mitogen-activated protein kinase and WRKY,an H2O2 burst,and the induction of jasmonic acid and abscisic acid signaling.The induced plants accumulated high levels of defenserelated chemicals,which possessed broad-spectrum anti-herbivore or anti-pathogen properties,and ultimately triggered resistance against Empoasca onukii and Colletotrichum fructicola in tea.We propose that these findings can supply an environmentally friendly management strategy for controlling an insect pest and a disease of tea plants.

Study on Building and Modeling of Virtual Data of Xiaosha River Artificial Wetland

From the viewpoint of systems science, this article takes Xiaosha River artificial wetland under planning and construction as object of study based on the systems theory and takes the accomplished and running project of Xinxuehe artificial wetland as reference. The virtual data of quantity and quality of inflow and the quality of outflow of Xiaosha River artificial wetland are built up according to the running experience, forecasting model and theoretical method of the reference project as well as the comparison analysis of the similarity and difference of the two example projects. The virtual data are used to study the building of forecasting model of BP neural network of Xiaosha River artificial wetland.

China’s role in scaling up energy storage investments

Accelerating the planning and development of a new power system that is more renewable energy-based is a strategic priority of achieving“dual carbon”goals(peaking carbon emissions before 2030 and becoming carbon neutral before 2060)in China.The large-scale development of energy storage technologies will address China’s flexibility challenge in the power grid,enabling the high penetration of renewable sources.This article intends to fill the existing research gap in energy storage technologies through the lens of policy and finance.Results indicate that policy uncertainties in renewable energy might undermine domestic investor confidence in energy storage technologies,while insufficient economic incentives may crowd out private sector participation.Drawing on international best practices,blended concessional finance,supported by development partners,can play a significant role in closing energy storage financing gaps in China and in countries of the Belt and Road Initiative(BRI).To deliver on China’s domestic and international climate commitments,this article makes three policy recommendations:(1)moving forward with a carbon pricing agenda that incentivizes energy storage investments in China;(2)tapping the potential of the domestic capital market to close financing gaps for novel energy storage technologies;(3)scaling up energy storage supply chains in BRI countries through multilateral cooperation.