The construction and understanding of synergy in well-defined dual-atom active sites is an available avenue to promote multistep tandem catalytic reactions. Herein, we construct a dual-hetero-atom catalyst that comprises adjacent Cu-N4 and Se-C3 active sites for efficient oxygen reduction reaction (ORR) activity. Operando X-ray absorption spectroscopy coupled with theoretical calculations provide in-depth insights into this dual-atom synergy mechanism for ORR under realistic device operation conditions. The heteroatom Se modulator can efficiently polarize the charge distribution around symmetrical Cu-N4 moieties, and serve as synergistic site to facilitate the second oxygen reduction step simultaneously, in which the key OOH*-(Cu1-N4) transforms to O*-(Se1-C2) intermediate on the dual-atom sites. Therefore, this designed catalyst achieves satisfied alkaline ORR activity with a half-wave potential of 0.905 V vs. RHE and a maximum power density of 206.5 mW cm−2 in Zn-air battery. 相似文献
An open tubular capillary electrochromatography column covalently bonded with polystyrene sulfonate was prepared via in situ polymerization using functionalized Azo-initiator 4,4′-Azobis(4-cyanopentanoyl chloride). Scanning electron, fluorescence, and atomic force microscopy techniques showed the formation of a relatively rough layer of polymer. In addition, –CN and C = O stretching vibrations from infrared spectroscopy proved the successful immobilization of the azo-initiator through covalent bonding and X-ray photoelectron spectroscopy confirmed the elemental composition of the formed polymer layer. The prepared column was found to be appropriate for small and medium-sized molecules separation. Compared to bare fused silica capillary column higher selectivity and resolution were obtained for the separation of alkaloids, sulfonamides, and peptides as a result of the electrostatic and pi-pi stacking interactions between the small organic molecules and the coated column without compromising the electroosmotic flow mobility. Separation efficiency was also increased compared to the bare capillary for the separation of alkaloids (about 1.5 times). Moreover, intraday, inter-day, intra-batch, and inter-batch relative standard deviation values of retention time and peak area of peptides were within 2% and 10%, respectively, indicating good repeatability of the column preparation procedure. The developed method for the covalent bonding of polymers through a functionalized azo-initiator could represent a promising stable method for the preparation of an open tubular column. 相似文献
Polyaniline/rare earth oxide composites (PANI/La2O3 and PANI/Sm2O3) were synthesized by in situ polymerization at the presence of sulfosalicylic acid (as dopant). The composites obtained were characterized by Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The thermal stability of the composites was investigated by thermogravimetry (TG) and derivative thermogravimetry (DTG). The electrochemical performance of the composites was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results of FTIR, XRD, SEM, CV, and EIS show that the structure of composite has changed greatly when rare earth oxide content is >0.7 g (PANI/La2O3[w/w(92.7/7.3)] and PANI/Sm2O3[w/w(96.2/3.8)]) and the PANI in the composite has transformed into pernigraniline base (non-conducting state) from emeraldine base (conducting state). TG-DTG analysis indicates that the thermal stability of composite was higher than pure PANI, which is attributed to the interaction between PANI and rare earth oxide. 相似文献
Controlling reaction selectivity is a permanent pursuit for chemists. Regioselective catalysis, which exploits and/or overcomes innate steric and electronic bias to deliver diverse regio‐enriched products from the same starting materials, represents a powerful tool for divergent synthesis. Recently, the 1,2‐Markovnikov hydroalkylation of 1,3‐dienes with simple hydrazones was reported to generate branched allylic compounds when a nickel catalyst was used. As part of the effort, shown here is that a complete switch of Markovnikov to anti‐Markovnikov addition is obtained by changing to a ruthenium catalyst, thus providing direct and efficient access to homoallylic products exclusively. Isotopic substitution experiments indicate that no reversible hydro‐metallation across the metal‐π‐allyl system occurred under ruthenium catalysis. Moreover, this protocol is applicable to the regiospecific hydroalkylation of the distal C=C bond of 1,3‐enynes. 相似文献
We have developed an unprecedented Pd‐catalyzed formal hydroalkylation of alkynes with hydrazones, which are generated in situ from naturally abundant aldehydes, as both alkylation reagents and hydrogen donors. The hydroalkylation proceeds with high regio‐ and stereoselectivity to form (Z)‐alkenes, which are more difficult to generate compared to (E)‐alkenes. The reaction is compatible with a wide range of functional groups, including hydroxy, ester, ketone, nitrile, boronic ester, amine, and halide groups. Furthermore, late‐stage modifications of natural products and pharmaceutical derivatives exemplify its unique chemoselectivity, regioselectivity, and synthetic applicability. Mechanistic studies indicate the possible involvement of Pd‐hydride intermediates. 相似文献
Phase estimation and compensation is one of the enabling functionalities in continous-variable quantum key distribution (CVQKD). Recently, a novel CVQKD scheme has been independently proposed to combat the local oscillator (LO) side channel attacks. Furthermore, we have carried out a proof-of-principle experimental study on the feasibility of the CVQKD without sending a LO. However, this scheme contains a serious weakness: The phase noise caused by the two different lasers between the sender and the receiver would severely destroy the quantum signal and finally reduce the secure distance. In this paper, we investigate the optical phase noise and explore the optimal approach to estimate and compensate such kind of noise with appropriate data overhead. Numerical simulations show that our scheme can successfully reconstruct the phase drifts even at low signal-to-noise ratio conditions. We also suggest that a higher accuracy of phase estimation could be achieved by using the frequency division multiplexing scheme. This opens an opportunity to employ advanced pilot-aided phase estimation techniques in quantum communication system.
A reconfigurable and stable mixer is proposed and demonstrated in this paper. It mainly consists of a dual-driven Mach–Zehnder modulator and a polarization modulator with several polarization controllers (PC) and polarizers (Pol). According to the theoretical analysis, different functions (such as single ended mixer, balanced mixer, I/Q mixer and image rejection mixer) can be realized by adjusting the PCs and Pols. The simulation results verify the possibility of multi-functions that realized by the reconfigurable mixer. In addition, another research on how the non-ideal parameters affect the image rejection ratio (ISR) and conversion efficiency of the mixer is also carried. The results show that both of them perform better as the extinction ratio gets higher. However, they are incurring a sharp decrease if the DC bias points deviate from the settled values. In the meantime, the results also indicate that the higher modulation indices lead to a better ISR. A 57.12 dB ISR can be achieved with conversion efficiency of ? 9.53 dB. 相似文献
Polyaniline (PANI)/CeO2 composites were prepared by adding CeO2 powder into the polymerization reaction mixture of aniline. Fourier transform infrared spectra (FTIR) and X-ray diffraction
(XRD) were used to characterize the composites. Thermogravimetry (TG) and derivative thermogravimetry (DTG) were used to study
the thermal stability of the composites. IR and XRD results show that interaction exists between PANI and CeO2. This interaction maybe is hydrogen bonding action between the hydroxyl groups on the surface of the CeO2 and the imine groups in the PANI molecular chains. TG–DTG analysis indicates that the thermal stability of the composites
is higher than that of the pure PANI. The improvement in the thermal stability of the composites is attributed to the interaction
between PANI and CeO2, which restricts the thermal motion of PANI chains and shields the degradation of PANI in the composites. 相似文献