Interfacial Proton Supply/Filtration Regulates the Dynamics of Electrocatalytic Nitrogen Reduction Reaction: A Perspective

As a promising energy carrier, ammonia synthesis by electrocatalytic nitrogen reduction reaction (eNRR) is a promising green and low-carbon ammonia synthesis strategy that can replace the traditional Haber–Bosch process. However, the development of eNRR processes is mainly severely constrained by competitive hydrogen evolution reaction (HER), and the corresponding strategies to inhibit this adverse side reaction to obtain high eNRR selectivity are still limited. In addition, for this complex reaction involving gas–liquid–solid three-phase interface and proton/electron transfer, it is great significance to analyze and summarize the existing inhibition HER strategies from the viewpoint of dynamics. In view of this, this work reviews proton supply/filtration regulation strategy in catalytic system, allowing a systematic survey of the literature focusing on interface membrane regulation (inorganic membrane and organic membrane), electrolyte regulation (metal-mediated strategy and electrolyte ion regulation strategy) and system device design (electrode structure design and electrolytic cell device design). Constructive catalytic system design guidance is also suggested to inhibit hydrogen evolution and improve NH₃ selectivity, aiming for scalable and economically feasible applications.     

Reaching the Fundamental Limitation in CO2 Reduction to CO with Single Atom Catalysts

The electrochemical CO₂ reduction reaction (CO₂RR) to value-added chemicals with renewable electricity is a promising method to decarbonize parts of the chemical industry. Recently, single metal atoms in nitrogen-doped carbon (MNC) have emerged as potential electrocatalysts for CO₂RR to CO with high activity and faradaic efficiency, although the reaction limitation for CO₂RR to CO is unclear. To understand the comparison of intrinsic activity of different MNCs, two catalysts are synthesized through a decoupled two-step synthesis approach of high temperature pyrolysis and low temperature metalation (Fe or Ni). The highly meso-porous structure results in the highest reported electrochemical active site utilization based on in situ nitrite stripping; up to 59±6% for NiNC. Ex situ X-ray absorption spectroscopy (XAS) confirms the penta-coordinated nature of the active sites. The catalysts are amongst the most active in the literature for CO₂ reduction to CO. The density functional theory calculations (DFT) show that their binding to the reaction intermediates approximates to that of Au surfaces. However, it is found that the turnover frequencies (TOFs) of the most active catalysts for CO evolution converge, suggesting a fundamental ceiling to the catalytic rates.     

Optimizing the Oxygen-Catalytic Performance of Zn–Mn–Co Spinel by Regulating the Bond Competition at Octahedral Sites

By using the more electro-negative Mn³⁺ ion to partially replace Co³⁺ at the octahedral site of spinel ZnCo₂O₄, i.e., forming ternary Zn–Mn–Co spinel oxide, the electrocatalytic oxygen reduction/evolution activity is found to be significantly increased. Considering the physical characterization and theoretical calculations, it demonstrated that the bond competition played a key role in regulating the cobalt valence state and the electrocatalytic activity. The partial replacement of octahedral-site-occupied Co³⁺ by Mn³⁺ can effectively modulate the adjacent Co–O bond and induce the Jahn–Teller effect, thus changing the originally stable crystal structure and optimizing the binding strength between the active center and reaction intermediates. Certainly, the Mn-substituted ZnMn_1.4Co_0.6O₄/NCNTs exhibit higher electrocatalytic oxygen reduction reaction (ORR) activity than that of ZnCo₂O₄/NCNTs and ZnMn₂O₄/NCNTs, supporting that the Co–O bond covalency determines the ORR activity of spinel ZnCo₂O₄. This study offers the competition between adjacent Co–O and Mn–O bonds via the B_Oh–O–B_Oh edge-sharing geometry. The ion substitution at octahedral sites by less electronegative cations can be a new and effective way to improve the electrocatalytic performance of cobalt-based spinel oxides.     

Pre-Activation of CO2 at Cobalt Phthalocyanine-Mg(OH)2 Interface for Enhanced Turnover Rate

Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO₂RR), but the molecule/substrate interaction is still pending for clarification and optimization to maximize the reaction kinetics. Herein, a CO₂RR catalyst is fabricated by affixing CoPc onto the Mg(OH)₂ substrate primed with conductive carbon, demonstrating an ultra-low overpotential of 0.31 ± 0.03 V at 100 mA cm⁻² and high faradaic efficiency of >95% at a wide current density range for CO production, as well as a heavy-duty operation at 100 mA cm⁻² for more than 50 h in a membrane electrode assembly. Mechanistic investigations employing in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectroscopy unravel that Mg(OH)₂ plays a pivotal role to enhance the CO₂RR kinetics by facilitating the first-step electron transfer to form anionic *CO₂⁻ intermediates. DFT calculations further elucidate that introducing Lewis acid sites help to polarize CO₂ molecules absorbed at the metal centers of CoPc and consequently lower the activation barrier. This work signifies the tailoring of catalyst-support interface at molecular level for enhancing the turnover rate of CO₂RR.     

Bifunctional Edge-Rich Nitrogen Doped Porous Carbon for Activating Oxygen and Sulfur

Oxygen reduction reaction (ORR) and sulfur reduction reaction (SRR) play key roles in advanced batteries. However, they both suffer from sluggish reaction kinetics. Here, an interesting nitrogen doped porous carbon material that can simultaneously activate oxygen and sulfur is reported. The carbon precursor is a nitrogen containing covalent organic framework (COF), constituting periodically stacked 2D sheets. The COF structure is well preserved upon pyrolysis, resulting in the formation of edge-rich porous carbon with structure resembling stacked holey graphene. The nitrogen containing groups in the COF are decomposed into graphitic and pyridinic nitrogen during pyrolysis. These edge sites and uniform nitrogen doping endow the carbon product with high intrinsic catalytic activities toward ORR and SRR. The COF derived carbon delivers outstanding performances when assembling as cathodes in the Li-S and Li-O₂ batteries. Simultaneous activation of oxygen and sulfur also enables a new battery chemistry. A proof-of-concept Li-S/O₂ hybrid battery is assembled, delivering a large specific capacity of 2,013 mAh g⁻¹. This study may inspire novel battery designs based on oxygen and sulfur chemistry.     

Understanding Boosted Selective CO2-to-CO Photoreduction with Pure Water Vapor over Hierarchical Biomass-Derived Carbon Matrix

Solar-driven CO₂ reduction reaction (CO₂RR) with water into carbon-neutral fuels is of great significance but remains challenging due to thermodynamic stability and kinetic inertness of CO₂. Biomass-derived nitrogen-doped carbon (N-C_b) have been considered as promising earth-abundant photocatalysts for CO₂RR, although their activities are not ideal and the reaction mechanism is still unclear. Herein, an efficient catalyst is developed for CO₂-to-CO conversion realized on diverse N-C_b materials with hierarchical pore structures. It is demonstrated that the CO₂-to-CO conversion preferentially takes place on positively charged carbon atoms next to pyridinic-N using two representatives treated pollens with the largest difference in pyridinic-N density and N content as model photocatalysts. Systematic experimental results indicate that surface local electric field originating from charge separation can be boosted by hierarchical pore structures, doped N, as well as pyridinic-N. Mechanistic studies reveal that positively charged carbon atoms next to pyridinic-N serve as active sites for CO₂RR, reduce the energy barrier on the formation of CO*, and facilitate the CO₂RR performance. All these benefits cooperatively contribute to treated chrysanthemum pollen catalyst exhibiting excellent CO formation rate of 203.2 µmol h⁻¹ g⁻¹ with 97.2% selectivity in pure water vapor. These results provide a new perspective into CO₂RR on N-C_b, which shall guide the design of nature-based photocatalysts for high-performance solar-fuel generation.     

一种具有宽带双极化低散射特征的微带阵列天线

针对阵列天线宽带散射缩减设计进行研究,设计了一种基于无源对消技术的低散射阵列天线,该新型微带阵列天线在宽频带内具有双极化低雷达散射截面（RCS, Radar Cross Section）性能;对基于两种散射性能不同的单元组成阵列的RCS性能进行了理论研究,进行了单元的散射幅度和相位对阵列RCS的影响分析;提出了一种加载T型缝隙的新型微带天线结构,该单元结构的辐射性能与散射性能能够进行独立调控和综合优化,该单元与传统微带贴片单元具有相似的辐射特性,并可在宽频带（带内和带外）内与传统微带单元产生有效相位差;将传统微带单元和加载T型缝隙的新型微带单元组成4×4阵列天线,仿真结果表明,提出的阵列天线在3GHz～7GHz（相对带宽80%）频带内实现了同极化RCS缩减,在3.3GHz～7GHz（相对带宽71.8%）频带内实现了交叉极化RCS缩减,缩减峰值分别为16.3dB和36.3dB,带内RCS缩减均值分别为14.1dB 和17.6dB;与传统微带阵列天线相比,提出的阵列天线增益下降小于0.1dB;提出的微带阵列天线具有高效率辐射和宽频带双极化低散射性能,为低散射阵列天线设计提供了新的思路。     

多源基因学习的微种群教与学优化及应用

由于微种群教与学优化算法的种群规模较小, 故其种群多样性很难维持. 为提高微种群教与学优化算法的搜索性能, 提出了一种基于多源基因学习的微种群教与学优化算法(micro-population teaching-learning-based optimization based on multi-source gene learning, MTLBO-MGL). 在MTLBO-MGL算法中, 将教阶段和学阶段根据随机选择策略来对个体进行基因水平上的进化操作; 并从基因层面上对种群多样性进行检测和使用稀疏谱聚类方法对种群的每个维度进行聚类. 然后, 根据多样性检测和聚类结果, 选择不同的进化策略来提高所提算法的搜索性能. 在28个测试函数上, 通过将所提算法与其他4种微种群进化算法作对比, 证明了所提算法的整体性能要显著好于所对比的4种算法. 本文还将所提算法应用于无人机三维路径规划问题, 结果表明MTLBO-MGL算法能够在该问题上取得较好结果.     

磁悬浮陀螺转子信号的局部均值分解降噪研究

磁悬浮陀螺转子电流信号对环境变化高度敏感,信号采样过程中不可避免会引入噪声,针对该问题提出一种基于局部均值分解（local mean decomposition, LMD）,融合豪斯多夫（Hausdorff）距离与阈值降噪（threshold denoising, TD）的算法以减弱噪声干扰。首先对原始信号进行局部均值分解,得到若干乘积函数（PF）分量和一个余量,然后根据各PF分量与原始信号间的豪斯多夫距离判定噪声、信号分量,再对噪声分量进行阈值处理,最后将阈值处理后的噪声分量、信号分量及余量进行叠加得到重构信号,实现陀螺仪转子电流信号的降噪。仿真实验结果表明,重构信号的信噪比相对于原始信号平均提高了12.86 db,均方根误差平均降低了9.25×10^-6 A;实测信号降噪结果表明,该降噪算法对四条导线边的滤波增益分别为40.0%、93.5%、30.8%和50.0%。     

基于 SVD-VMD 和 SVM 滚动轴承故障诊断方法

针对故障滚动轴承振动信号中含有干扰信号,难以准确提取出故障信息,提出了一种基于奇异值分解(SVD)、变分模态分解(VMD)、和支持向量机(SVM)的滚动轴承故障诊断方法。首先利用奇异值分解对信号进行处理,根据奇异值峰度差分谱来确定分解后重构矩阵的有效阶数,然后根据该有效阶数重构信号,对重构后的信号进行VMD分解,根据上述有效阶数确定分解的本征模态函数(IMF)分量的个数,从分解后的IMF分量中提取故障特征参数,将其作为支持向量机的输入参数进行故障诊断。最后采用合肥工业大学轴承试验机进行验证,并与直接进VMD分解及基于带通滤波器信号去噪的故障诊断方法进行对比,结果表明该方法能有效识别滚动轴承的故障类型,可用于滚动轴承故障诊断。