d-Orbital Reconstructions Forced by Double Bow-Shaped Deformations and Second Coordination Sphere Effects of Cu(II) Heme Analogs in HER**

Both geometric architecture and electronic configurations of heme proteins contribute to its activity. In this work we designed and synthesized a series of four copper(II) porphyrin complexes ( 4 -, 3 -, 2 - and 1 -Cu) where the molecular conformations are modulated by a pair of stepwise shortened straps on the same porphyrin side (cis-ortho) to give double bow-shaped skeletons. Single crystal structures demonstrate that the straps gradually increase the saddle deformation and the deviation of the metal centers, which is in accordance with two, unusual d-orbital reconstructions of two different ground states, as revealed by 4 K EPR and DFT calculations. In the study of the electrocatalytic hydrogen evolution reaction (HER), 1 -Cu, with the shortest straps, showed the most apparent improvement of activity. Second coordination sphere (SCS) effects created by the double bow-shaped architecture and the strong saddle porphyrin core in 1 -Cu are found to play key roles in proton trapping during the catalytic process. The work contributes a novel strategy to improve the catalytic performance of heme analogs through ligand geometric modulation.     

“翻转+分段式”有机化学实验教学设计及实践研究

以FeCl3·6H2O催化合成乙酸乙酯为教学内容,采用“翻转+分段式”混合教学方法对整个实验过程进行了改革探索。通过教师准备学习资源,学生自主学习,课堂分段讲解,互动交流以及跟踪评价等,探讨了大学有机化学实验实施“翻转+分段式”混合教学方法的有效途径。实践结果表明:混合教学模式能够显著促进学生对实验内容的理解和掌握,明显增加学生自主操作的时间,还能有效降低实验过程中的安全隐患。     

DMF体系中Cu2O球晶的制备及形貌分析

以N,N-二甲基甲酰胺(DMF)为溶剂,通过改变铜源和表面活性剂,调控反应参数,溶剂热条件下制备了三维十字形、空心及实心的Cu₂O球晶。利用XRD、SEM等表征手段,分析探讨了工艺条件变化对Cu₂O球晶形貌的影响。研究表明,随着DMF浓度的增大,体系的还原能力增强,Cu⁺增多,溶液的过饱和度增大,Cu₂O晶体集合体形态由晶体结构控制的各向异性与对称性的球晶逐渐向各向同性球晶演变。十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTAB)、聚乙烯吡咯烷酮(PVP)等表面活性剂有助于降低溶液的过饱和度,增加结晶质的表面扩散能力,有利于规则形态Cu₂O晶粒的形成。反应体系中,Cu(Ac)₂·H₂O水解生成的羧基与DMF中的甲酰基在高温下发生脱羧反应产生CO₂气体以及SDS发泡作用产生的气体是形成空心Cu₂O球晶的重要原因。     

Tuning the CO2 Hydrogenation Selectivity of Rhodium Single-Atom Catalysts on Zirconium Dioxide with Alkali Ions

Tuning the coordination environments of metal single atoms (M₁) in single-atom catalysts has shown large impacts on catalytic activity and stability but often barely on selectivity in thermocatalysis. Here, we report that simultaneously regulating both Rh₁ atoms and ZrO₂ support with alkali ions (e.g., Na) enables efficient switching of the reaction products from nearly 100 % CH₄ to above 99 % CO in CO₂ hydrogenation in a wide temperature range (240–440 °C) along with a record high activity of 9.4 mol_CO g_Rh⁻¹ h⁻¹ at 300 °C and long-term stability. In situ spectroscopic characterization and theoretical calculations unveil that alkali ions on ZrO₂ change the surface intermediate from formate to carboxy species during CO₂ activation, thus leading to exclusive CO formation. Meanwhile, alkali ions also reinforce the electronic Rh₁-support interactions, endowing the Rh₁ atoms more electron deficient, which improves the stability against sintering and inhibits deep hydrogenation of CO to CH₄.     

新型N-杂环取代查尔酮衍生物的合成

以4-二甲氨基苯甲醛与4'-氟苯乙酮为原料,经羟醛缩合反应制得4-二甲氨基-4'-氟查尔酮(1);1分别与咪唑、哌嗪等含氮杂环化合物经取代反应合成了6个新型的N-杂环取代查尔酮衍生物,其结构经1H NMR,13C NMR和IR表征。     

基于双功能单体的磁性双酚A印迹聚合物的制备及应用

以二氧化硅包覆的四氧化三铁为载体,双酚A(BPA)为模板分子,β-环糊精和4-乙烯基吡啶为二元功能单体,采用热聚合方法制备了对双酚A具有特异吸附性能的磁性印迹复合材料(mag-MIPs).采用透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)和振动样品磁强计(VSM)对该印迹复合材料进行了表征,并结合磁固相萃取(M-SPE)技术和高效液相色谱(HPLC)研究了其对双酚A的吸附行为,结果表明该印迹复合材料对双酚A具有良好的选择吸附能力.液相色谱检测结果表明,该磁性印迹复合材料可用于环境水样中双酚A的快速分离富集,回收率为90.51%~98.21%.     

地下水中102种酸性、碱性和中性有机污染物的气相色谱-质谱法同时快速测定

建立了同时快速检测地下水中102种酸性、碱性和中性有机污染物的气相色谱－质谱（GC－MS）分析方法,所建方法涉及苯酚、苯胺、苯基醚、多氯萘、联苯等10类污染物。考察了酸性、碱性和中性有机污染物的同时提取条件,结果显示采用先中性、再酸性、后碱性三步液液萃取方式可以改善污染物的提取回收率,提高分析准确度和精密度。在优化条件下,除五氯苯酚外,101种目标物在各自的质量浓度范围内呈良好线性关系,相关系数（r）为0.995 0～0.999 9。地下水样品在低、中、高3个浓度水平的加标回收率分别为47.2%～126%、43.0%～117%、38.8%～120%,相对标准偏差（RSD,n = 7）分别为1.1%～27%、2.6%～33%、2.9%～30%,方法检出限为1.8～19.7 ng/L（五氯苯酚、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二（2-乙基）己酯除外）。方法应用于山西、河南等部分典型污染场地的地下水样品筛查,检出苯酚、苯胺、多环芳烃及其衍生物等24种酸、碱和中性有机污染物,点位检出率达到46.7%,水质明显呈点源污染特征。该方法灵敏、准确、简单、快速,可实现多目标物同时检测,有助于地下水中有机污染物快速筛查。     

气相色谱-质谱法测定地下水中多氯萘

建立了地下水中1-氯萘、2-氯萘、1,4-二氯萘、1,2,3,4-四氯萘、1,3,5,7-四氯萘、1,2,3,5,7-五氯萘、1,2,3,5,6,7-六氯萘、1,2,3,4,5,6,7-七氯萘和八氯萘9种多氯萘(PCNs)的气相色谱-质谱(GC-MS)分析方法。对比研究了液液萃取(LLE)和固相萃取(SPE)萃取地下水中PCNs的提取效率,优选二氯甲烷-液液萃取为PCNs检测的前处理方法。在优化条件下,9种PCNs的线性范围为5~100μg/L,各组分的相关系数(r)大于0.995,方法检出限(S/N=3)为4.21~7.41 ng/L,地下水的平均加标回收率为70.7%~112%,相对标准偏差(RSD,n=5)均小于9.9%。该方法已用于地下水样中多氯萘的检测。     

Single layer graphitic carbon nitride-modified graphene composite as a fiber coating for solid-phase microextraction of polycyclic aromatic hydrocarbons

The authors describe a three-dimensional single layer graphitic carbon nitride-modified graphene composite (g-C₃N₄@G) deposited on a stainless steel wire by a sol-gel technique. The coated fiber was applied to direct immersion solid-phase microextraction of trace levels of polycyclic aromatic hydrocarbons (PAHs) from cosmetics samples prior to their determination by gas chromatography with mass spectrometry (GC-MS). Due to π stacking interaction and hydrophobic interaction between the g-C₃N₄@G coating and the analytes (naphthalene, acenaphthene, fluorene, phenanthrene, fluoranthene and pyrene), the fiber displays an excellent adsorption capability for the analytes. Under optimized conditions, the method has a wide linear range, low LODs (from 1.0 to 2.0 ng L⁻¹), good repeatability and high recoveries. It was successfully applied to the determination of PAHs in cosmetics. The g-C₃N₄@G fiber also exhibited good durability.

Schematic of a three-dimensional single layer graphitic carbon nitride-modified graphene composite (g-C₃N₄@G) that was coated onto a stainless steel wire for the direct-immersion solid phase microextraction of trace levels of polycyclic aromatic hydrocarbons prior to gas chromatography-mass spectrometric detection.