Simultaneous CO2 and H2O Activation via Integrated Cu Single Atom and N Vacancy Dual-Site for Enhanced CO Photo-Production

Photocatalytic conversion of CO₂ into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO₂ photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO₂ reduction and H₂O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu₁/N_2CV-CN). Experimental and theoretical results show that Cu single-atom centers promote CO₂ chemisorption and activation via accumulating photogenerated electrons, and the N_2CV sites enhance the dissociation of H₂O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu₁/N_2CV-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g⁻¹ h⁻¹. An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO₂ photoreduction process.     

Orthogonal array design (OAD) for the optimization of mercury extraction from soils by dilute acid with microwave heating

The use of dilute acid for mercury extraction from geological samples with microwave assisted heating was investigated. An orthogonal array design OA(16)(4(1)x2(12)) was applied to select the optimum conditions. The effects of the concentration of HNO(3), the additions of HCl and H(2)S0(4), the extraction time and their interactions were evaluated by the mixed-level orthogonal array design (OAD). The results indicated that the addition of small amount of HCl would improve significantly the extraction of mercury from soil matrices. From the study, it is seen that the mercury in the soil matrices could be extracted completely by 14% (v/v) HNO(3) with small quantity of HCl. The effects of the pressure within the digestion vessel and the sample mass were studied under the optimum conditions derived from the OAD. The extraction methods with optimum conditions were evaluated by determining mercury in NIST SRM 1645 River Sediment, NIES CRM No. 2 Pond Sediment and NRCC BCSS-1 Marine Sediment. Recoveries of 78-109% were achieved. Good mean recoveries of 95-98% were also obtained from real soil samples spiked with different species of mercury.     

对“微波共振跃迁法测量电子偶素2~3S_1-2~3P_1精细结构”实验拟合公式的探讨

本文对Michigan大学S.Hatamian等人在“微波共振跃迁法测量电子偶素2~3S_1-2~3P_J精细结构”实验中所用拟合公式进行了审慎的分析和推证,修正了该公式的功率增宽项,并就Mainz大学R.Ley等人对该公式的批评作了评价。最后,采用新、旧拟合公式对Michigan组实验数据进行拟合并讨论其结果。     

Ion solvation by channel carbonyls characterized by 17O solid-state NMR at 21 T

Recently available ultrahigh magnetic fields offer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of second-order quadrupole interactions. Here, we present a new approach for understanding the function and energetics of ion solvation in channels using solid-state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A. The chemical shift and quadrupole coupling parameters obtained in powder samples of lyophilized material are similar to those shown in the literature for carbonyl oxygens. In lipid bilayers, it is found that the carbonyl 17O anisotropic chemical shift of Leu10, one of the three carbonyl oxygens contributing to the ion binding site in gramicidin A, is altered by 40 ppm when K+ ion binds to the channel, demonstrating a high sensitivity to such interactions. Moreover, considering the large breadth of the carbonyl 17O chemical shift (>500 ppm), the recording of anisotropic 17O chemical shifts in bilayers aligned with respect to magnetic field B0 offers high-quality structural restraints similar to 15N and 13C anisotropic chemical shifts.     

某些苯二醛类双Schiff碱及其双铜(Ⅱ)配合物研究

用2-甲氧基-5-氯-1,3-苯二甲醛与含有不同取代基团X的邻氨基酚缩合,合成了一系列双Schiff碱L-X(X=OMe,diMe,Me,t-Bu,H,Cl,NO_2),它们与乙酸铜(Ⅱ)作用生成了一系列的双核配合物Cu_2L-X(OEt).用红外、紫外、磁天平、顺磁共振等手段对配合物进行了表征,并通过量化计算(CNDO/2法)探讨了配合物的成键性质。研究结果表明,该类配合物是一个较大的共轭体系,配合物中Cu(Ⅱ).Cu(Ⅱ)之间有较强的反铁磁性交换作用,其共轭程度和交换作用强弱皆随X基团的不同而呈现某种变化规律。