Three compounds with nitrocarbazole frameworks were synthesized and their electrochemical reversibility as organic electrocatalysts was studied by cyclic voltammetry. The electrochemical reversibility and oxidation‐r...Three compounds with nitrocarbazole frameworks were synthesized and their electrochemical reversibility as organic electrocatalysts was studied by cyclic voltammetry. The electrochemical reversibility and oxidation‐reduction potential of the compounds were greatly affected by their substituents. The oxidation‐reduction potential of the compound with an electron‐donating group was negative, while that of the compound with an electron‐withdrawing group on the carbazole framework was positive. The electrocatalytic oxidation activities of the nitrocarbazole compounds were investigated through cyclic voltammetry and controlled potential electrolysis at room tem‐perature. The electrocatalysts showed excellent selectivity for p‐methoxybenzyl alcohol, converting it to the corresponding aldehyde through electro‐oxidation with just 2.5 mol%of the electrocata‐lysts presented. The electrocatalysts maintained their excellent electroredox activity following re‐cycling.展开更多
The development of high efficiency and stable electrocatalysts for oxygen evolution is critical for energy storage and conversion systems. Herein, a series of Co/Fe bimetal-organic frameworks (MOFs) were fabricated us...The development of high efficiency and stable electrocatalysts for oxygen evolution is critical for energy storage and conversion systems. Herein, a series of Co/Fe bimetal-organic frameworks (MOFs) were fabricated using a facile ultrasonic method at room temperature, as electrocatalysts for the oxygen evolution reaction (OER) in alkaline solution. The Co2Fe-MOF exhibited an overpotential of 280 mV at a current density of 10 mA cm^-2, a low Tafel slope of 44.7 mV dec^-1, and long-term stability over 12000 s in 1 mol L^-1 KOH. This impressive performance was attributed to the high charge transfer rate, large specific surface area, and synergistic effects of the cobalt and iron centers.展开更多
Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical...Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones(such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C–H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.展开更多
Porous organic polymers(POPs) have recently emerged as promising candidates for catalyzing oxygen reduction reaction(ORR).Compared to conventional Pt-based ORR catalysts, these newly developed porous materials, includ...Porous organic polymers(POPs) have recently emerged as promising candidates for catalyzing oxygen reduction reaction(ORR).Compared to conventional Pt-based ORR catalysts, these newly developed porous materials, including both non-precious metal based catalysts and metal-free catalysts, are more sustainable and cost-effective. Their porous structures and large surface areas facilitate mass and electron transport and boost the ORR kinetics. This mini-review will give a brief summary of recent development of POPs as electrocatalysts for the ORR. Some design principles, different POP structures, key factors for their ORR catalytic performance, and outlook of POP materials will be discussed.展开更多
基金supported by the Special Program for the National Basic Research Program of China(973 Program,2012CB722604)~~
文摘Three compounds with nitrocarbazole frameworks were synthesized and their electrochemical reversibility as organic electrocatalysts was studied by cyclic voltammetry. The electrochemical reversibility and oxidation‐reduction potential of the compounds were greatly affected by their substituents. The oxidation‐reduction potential of the compound with an electron‐donating group was negative, while that of the compound with an electron‐withdrawing group on the carbazole framework was positive. The electrocatalytic oxidation activities of the nitrocarbazole compounds were investigated through cyclic voltammetry and controlled potential electrolysis at room tem‐perature. The electrocatalysts showed excellent selectivity for p‐methoxybenzyl alcohol, converting it to the corresponding aldehyde through electro‐oxidation with just 2.5 mol%of the electrocata‐lysts presented. The electrocatalysts maintained their excellent electroredox activity following re‐cycling.
基金supported by the National Natural Science Foundation of China(21872016)the Fundamental Research Funds for the Central Universities(DUT17ZD204)~~
文摘The development of high efficiency and stable electrocatalysts for oxygen evolution is critical for energy storage and conversion systems. Herein, a series of Co/Fe bimetal-organic frameworks (MOFs) were fabricated using a facile ultrasonic method at room temperature, as electrocatalysts for the oxygen evolution reaction (OER) in alkaline solution. The Co2Fe-MOF exhibited an overpotential of 280 mV at a current density of 10 mA cm^-2, a low Tafel slope of 44.7 mV dec^-1, and long-term stability over 12000 s in 1 mol L^-1 KOH. This impressive performance was attributed to the high charge transfer rate, large specific surface area, and synergistic effects of the cobalt and iron centers.
基金supported by the National Natural Science Foundation of China (21821002, 21772222, and 91956112)Chinese Academy of Sciences (XDB20000000)Science and Technology Commission of Shanghai Municipality (18JC1415600 and 20JC1417100)。
文摘Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones(such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C–H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.
文摘Porous organic polymers(POPs) have recently emerged as promising candidates for catalyzing oxygen reduction reaction(ORR).Compared to conventional Pt-based ORR catalysts, these newly developed porous materials, including both non-precious metal based catalysts and metal-free catalysts, are more sustainable and cost-effective. Their porous structures and large surface areas facilitate mass and electron transport and boost the ORR kinetics. This mini-review will give a brief summary of recent development of POPs as electrocatalysts for the ORR. Some design principles, different POP structures, key factors for their ORR catalytic performance, and outlook of POP materials will be discussed.