巯基卟啉自组装膜的制备及应用研究进展

详细介绍了巯基卟啉自组装膜的几种制备方法,评述了不同制备方法的优缺点;对卟啉自组装膜在电荷转移、分子氧电催化、分子光电器件等领域的研究进展进行了评述,引用文献54篇。

Efficient photoelectrocatalytic CO_2 reduction by cobalt complexes at silicon electrode

Two homogeneous photoelectrocatalytic systems composed of simple polypyridyl Co complexes[Co(tpy)2](PF6)2and[Co(bpy)3](PF6)2as electrocatalysts and a Si wafer as the photoelectrode were used for combined photoelectrochemical reduction of CO2to CO.A high photocurrent density of1.4mA/cm2was observed for the system with the[Co(tpy)2](PF6)2catalyst and a photovoltage of400mV was generated.Faradaic efficiencies of CO were optimized to83%and94%for the[Co(tpy)2](PF6)2and[Co(bpy)3](PF6)2complexes,respectively,in acetonitrile solution with10%methanol(volume fraction,same below)as a protic additive.Addition of2%water volume fraction induced a large amount of non‐specific H2evolution by the Si photoelectrode.

Alkali metal cation effects on electrocatalytic CO_(2)reduction with iron porphyrins

The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali metal cations such as sodium and potassium.Although considerable efforts havebeen made to design efficient electrocatalysts for CO_(2)RR and to investigate the structure–activityrelationships using molecular model complexes,only a few studies have been investigated the effectof alkali metal cations on electrocatalytic CO_(2)RR.In this study,we report the effect of alkali metalcations(Na^(+)and K^(+))on electrocatalytic CO_(2)RR with Fe porphyrins.By running CO_(2)RR electrocatalysisin dimethylformamide(DMF),we found that the addition of Na^(+)or K^(+)considerably improves thecatalytic activity of Fe chloride tetrakis(3,4,5‐trimethoxyphenyl)porphyrin(FeP).Based on thisresult,we synthesized an Fe porphyrin^(N)18C6‐FeP bearing a tethered 1‐aza‐18‐crown‐6‐ether(^(N)18C6)group at the second coordination sphere of the Fe site.We showed that with the tethered^(N)18C6 to bind Na^(+)or K^(+),^(N)18C6‐FeP is more active than FeP for electrocatalytic CO_(2)RR.This workdemonstrates the positive effect of alkali metal cations to improve CO_(2)RR electrocatalysis,which isvaluable for the rational design of new efficient catalysts.

Insight on the active sites of CoNi alloy embedded in N-doped carbon nanotubes for oxygen reduction reaction

Transition metal alloy electrocatalysts have sparked intense interest for their use in oxygen reduction reaction(ORR).However,there is almost no corresponding research on the alloy active sites.In this study,CoNi alloy nanoparticles embedded in bamboo-like N-doped carbon nanotubes(CoNi-NCTs)as catalysts constructed by a facile pyrolysis of Prussian blue analogs were investigated.The density functional theory calculation reveals that the oxygen molecules are more easily adsorbed on the Ni sites in these catalysts,while the Co sites favor the formation of OOH★intermediates during ORR.In addition,the cooperation of the CoNi alloys with the N-doped carbon benefits electron transfer and promotes electrocatalytic activity.The optimized CoNi-NCT shows remarkable ORR catalytic activity with an half-wave potential(E1/2)of 0.83 V,an onset potential(Eonset)of 0.97 V,and superior durability,all of which surpass the commercial Pt/C catalysts.The assembled zinc-air battery delivers a small charge/discharge voltage gap of 0.86 V at 10 mA cm^(-2),a high-power density of 167 mW cm^(-2),and good stability(running stably over 900 cycles).

Promoted porous Co_3O_4-Al_2O_3 catalysts for ammonia decomposition

Transition metal catalysts have been considerably used for NH3 decomposition because of the potential application in COx-free H2 generation for fuel cells. However, most transition metal catalysts prepared via traditional synthetic approaches performed the inferior stability due to the agglomeration of active components. Here, we adopted an efficient method, aerosol-assisted self- assembly approach （AASA）, to prepare the optimized cobalt-alumina （C0304-A1203） catalysts. The C0304-A1203 catalysts exhibited excellent catalytic performance in the NH3 decomposition reaction, which can reach 100% conversion at 600 ℃and maintain stable for 72 h at a gaseous hourly space velocity （GHSV） of 18000 cm3 gcat-1 h-1. The catalysts were characterized by various techniques including transmission electron microscope （TEM）, scanning electron microscope （SEM）, nitrogen sorption, temperature-programmed reduction by hydrogen （H2-TPR）, ex-situ/in-situ Raman and ex-situ/in-situ X-ray diffraction （XRD） to obtain the information about the structure and property of the catalysts. H2-TPR and in-situ XRD results show that there is strong interaction between the cobalt and alumina species, which influences the redox properties of the catalysts. It is found that even a low content of alumina （10 at%） is able to stabilize the catalysts due to the adequate dispersion and rational interaction between different components, which ensures the high activity and superior stability of the cobalt-alumina catalysts.