2D sp2 Carbon‐Conjugated Porphyrin Covalent Organic Framework for Cooperative Photocatalysis with TEMPO

2D covalent organic frameworks (COFs) are receiving ongoing attention in semiconductor photocatalysis. Herein, we present a photocatalytic selective chemical transformation by combining sp² carbon‐conjugated porphyrin‐based covalent organic framework (Por‐sp²c‐COF) photocatalysis with TEMPO catalysis illuminated by 623 nm red light‐emitting diodes (LEDs). Highly selective conversion of amines into imines was swiftly afforded in minutes. Specifically, the π‐conjugation of porphyrin linker leads to extensive absorption of red light; the sp² ?C=C? double bonds linkage ensures the stability of Por‐sp²c‐COF under high concentrations of amine. Most importantly, we found that crystalline framework of Por‐sp²c‐COF is pivotal for cooperative photocatalysis with (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO). This work foreshadows that the outstanding hallmarks of COFs, particularly crystallinity, could be exploited to address energy and environmental challenges by cooperative photocatalysis.     

π‐Interactions between Cyclic Carbocations and Aromatics Cause Zeolite Deactivation in Methanol‐to‐Hydrocarbon Conversion

The understanding of catalyst deactivation represents one of the major challenges for the methanol‐to‐hydrocarbon (MTH) reaction over acidic zeolites. Here we report the critical role of intermolecular π‐interactions in catalyst deactivation in the MTH reaction on zeolites H‐SSZ‐13 and H‐ZSM‐5. π‐interaction‐induced spatial proximities between cyclopentenyl cations and aromatics in the confined channels and/or cages of zeolites are revealed by two‐dimensional solid‐state NMR spectroscopy. The formation of naphtalene as a precursor to coke species is favored due to the reaction of aromatics with the nearby cyclopentenyl cations and correlates with both acid density and zeolite topology.     

Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH4 Conversion to Syngas

Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electrocatalysis, photocatalysis, and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self‐strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox‐active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies.     

Strain Influences the Hydrogen Evolution Activity and Absorption Capacity of Palladium

Strain engineering can increase the activity and selectivity of an electrocatalyst. Tensile strain is known to improve the electrocatalytic activity of palladium electrodes for reduction of carbon dioxide or dioxygen, but determining how strain affects the hydrogen evolution reaction (HER) is complicated by the fact that palladium absorbs hydrogen concurrently with HER. We report here a custom electrochemical cell, which applies tensile strain to a flexible working electrode, that enabled us to resolve how tensile strain affects hydrogen absorption and HER activity for a thin film palladium electrocatalyst. When the electrodes were subjected to mechanically‐applied tensile strain, the amount of hydrogen that absorbed into the palladium decreased, and HER electrocatalytic activity increased. This study showcases how strain can be used to modulate the hydrogen absorption capacity and HER activity of palladium.     

2020 Roadmap on Carbon Materials for Energy Storage and Conversion

Carbon is a simple, stable and popular element with many allotropes. The carbon family members include carbon dots, carbon nanotubes, carbon fibers, graphene, graphite, graphdiyne and hard carbon, etc. They can be divided into different dimensions, and their structures can be open and porous. Moreover, it is very interesting to dope them with other elements (metal or non‐metal) or hybridize them with other materials to form composites. The elemental and structural characteristics offer us to explore their applications in energy, environment, bioscience, medicine, electronics and others. Among them, energy storage and conversion are extremely attractive, as advances in this area may improve our life quality and environment. Some energy devices will be included herein, such as lithium‐ion batteries, lithium sulfur batteries, sodium‐ion batteries, potassium‐ion batteries, dual ion batteries, electrochemical capacitors, and others. Additionally, carbon‐based electrocatalysts are also studied in hydrogen evolution reaction and carbon dioxide reduction reaction. However, there are still many challenges in the design and preparation of electrode and electrocatalytic materials. The research related to carbon materials for energy storage and conversion is extremely active, and this has motivated us to contribute with a roadmap on ‘Carbon Materials in Energy Storage and Conversion’.     

Preparation of N-acetyl-para-aminophenol via a flow route of a clean amination and acylation of p-nitrophenol catalyzing by core-shell Cu2O@CeO2

The selectivity and reactivity to converse series nitroaromatic into aminobenzenes are especially significant, which play a vital role in synthesizing required drugs or other fine chemicals. Herein, p-nitrophenol (p-NP) has been completely conversed into p-anomiphenol (p-AP) with a high activity factor k (0.033 s⁻¹·mg⁻¹) and reusability by core-shell Cu₂O@CeO₂ catalyst. N-acetyl-para-aminophenol (paracetamal, APAP) as a model drug was further synthesized via a flow route proceeded in two steps including p-NP reduction and subsequently p-AP acylation with self-constructing device. The yield of the paracetamal is up to 85% with a highly purity. The mechanism investigation justifies the rich-electron centers and cation defects generated from the redox coupled Cu⁺→Cu⁰ with Ce³⁺→Ce⁴⁺ will steer selective conversion of p-NP to p-AP, a rate-determining step in the production of APAP. The present results could visualize a highly selective catalyst and a new synthesis route for pharmaceuticals such as paracetamal by using nitroaromatic compounds as the raw materials with environment-friendly, low-cost, easy-manipulation, high-efficiency and high purity.     

Recent Developments in Carbon-Based Nanocomposites for Fuel Cell Applications: A Review

Carbon-based nanocomposites have developed as the most promising and emerging materials in nanoscience and technology during the last several years. They are microscopic materials that range in size from 1 to 100 nanometers. They may be distinguished from bulk materials by their size, shape, increased surface-to-volume ratio, and unique physical and chemical characteristics. Carbon nanocomposite matrixes are often created by combining more than two distinct solid phase types. The nanocomposites that were constructed exhibit unique properties, such as significantly enhanced toughness, mechanical strength, and thermal/electrochemical conductivity. As a result of these advantages, nanocomposites have been used in a variety of applications, including catalysts, electrochemical sensors, biosensors, and energy storage devices, among others. This study focuses on the usage of several forms of carbon nanomaterials, such as carbon aerogels, carbon nanofibers, graphene, carbon nanotubes, and fullerenes, in the development of hydrogen fuel cells. These fuel cells have been successfully employed in numerous commercial sectors in recent years, notably in the car industry, due to their cost-effectiveness, eco-friendliness, and long-cyclic durability. Further; we discuss the principles, reaction mechanisms, and cyclic stability of the fuel cells and also new strategies and future challenges related to the development of viable fuel cells.     

参变过程中的群速延迟对晶体匹配长度的影响

基于能量守恒和三波耦合波方程,建立了超短脉冲在参变过程中二次谐波产生时的I类和II类相位匹配条件、基波与谐波之间的群速延迟时间、以及群速失配对晶体长度限制的理论基础。以负单轴非线性光学晶体CsLiB6O10为例,分析和数值计算了超短脉冲宽度为100fs时,谐波的群速匹配长度随基波波长变化的规律。研究结果表明在I类相位匹配条件下,基波波长为642nm时,群速延迟最小,相应的群速匹配晶体长度最长为19.1mm;在II类相位匹配条件下,基波波长为767nm,群速延迟最小,群速匹配长度最长为0.89mm。     

自启动的非归零/归零码和光电时钟信号发生器及码型转换

采用双波长注入一包含伪随机码发生器与相位调制器的光电振荡器可以同时得到非归零(NRZ)码,归零(RZ)码以及光,电时钟信号输出。该方案使用了光域耦合的双环路结构,在不增加有源器件的条件下实现边模抑制。相位调制器用于反馈调制并同时实现占空比可调的非归零码到归零码的转换。双波长的注入排除了编码信号在振荡器中引入的非时钟频率成分。实验给出了10 Gb/s工作速率下的结果,得到了抖动为637 fs的光信号输出。转换得到的归零码信号占空比约为33%。输出电时钟信号的相位噪声在频偏10 kHz处为-109 dBc/Hz,边模抑制比为58 dB。