Carbon-zinc-cobalt-supported zinc phthalocyanide heterojunction catalyst for double-light reduction of co 2 Methods

A technology of zinc phthalocyanide and heterojunction is applied in the field of conversion and utilization of greenhouse gas CO2, which can solve the problems of difficult large-scale application, many organic acid products, and reduced reaction yield, so as to improve the overall conversion efficiency and improve separation. Efficiency, the effect of improving selectivity

Active Publication Date: 2020-05-12
ZHEJIANG UNIV
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Problems solved by technology

[0003] Takayama Tomoaki et al. Using metal sulfides and RGO-TiO in a Z-type reactor 2 Photoreduction of CO as a catalyst 2 reaction, the study found that CuGaS 2 Catalyst for CO 2 Reduction to CO has a strong catalytic effect, but CO, as a toxic substance, can easily cause catalyst poisoning, resulting in a decrease in reaction yield
Cheng Jun et al. developed a three-dimensional copper foam-supported graphene as the cathode and titanium dioxide nanotubes as the photoanode for photoreduction of CO 2 Reaction system, simultaneous application of light and external bias improves the conversion efficiency, but the reaction selectivity is poor and the organic acid product is more
ShyamKattel et al. compared three platinum-containing catalysts for CO 2 Catalysis of the reduction, showing that Pt / TiO 2 Co-catalyst for CH 4 Strong selectivity for formation, but poor catalyst economy due to higher price of precious metal platinum
HeHaiying et al. studied the reduction of CO by graphene-based single-atom catalysts 2 reaction, indicating that the catalyst containing copper single atoms has strong catalytic performance, but the synthesis process of the catalyst is complicated and difficult to be applied on a large scale
[0004] Currently CO 2 Due to the low conversion efficiency and poor product selectivity of the catalytic reduction reaction, it is urgent to develop efficient CO 2 Reduction reaction system and innovative catalyst materials
Reduction of CO in double light 2 The combination of heterojunction catalysts in the system can effectively improve the conversion of light energy into electrical energy and CO 2 Conversion to liquid fuel selectivity with strong CO 2 The application prospect of transformation and utilization to produce chemicals, but there is no literature report on this aspect

Method used

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  • Carbon-zinc-cobalt-supported zinc phthalocyanide heterojunction catalyst for double-light reduction of co <sub>2</sub> Methods
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Embodiment 1

[0037] Take 1g of zinc-cobalt imidazole framework (Zn / Co ZIF) (average diameter 500nm) and put it into a tube furnace, and raise the temperature to 600°C at 5°C / min in a mixed gas of nitrogen and hydrogen (nitrogen 50vol%+hydrogen 50vol%) , and heated at constant temperature for 3 hours to obtain a calcined product. The calcined product was mixed with 0.1g of zinc phthalocyanide (purchased from Sinopharm Group), fully ground and added to 50ml of tetrahydrofuran liquid (purchased from Sinopharm Group), and heated at 80°C in a magnetically stirred oil bath to evaporate all the liquid. The solids obtained after evaporation were mixed, then placed in a muffle furnace to raise the temperature to 300°C at 5°C / min, and calcined at a constant temperature for 2 hours to prepare a carbon-zinc-cobalt-supported zinc phthalocyanide heterojunction catalyst. Take 10 mg of this catalyst, 100 μL of deionized water, and 200 μL of Nafion solution (purchased from DuPont) with a mass concentration...

Embodiment 2

[0039] Take 10g of zinc-cobalt imidazole framework (Zn / Co ZIF) (average diameter 500nm) and put it into a tube furnace, and raise the temperature to 600°C at 5°C / min in a mixed gas of nitrogen and hydrogen (nitrogen 50vol%+hydrogen 50vol%) , and heated at constant temperature for 3 hours to obtain a calcined product. Mix the calcined product with 1g of zinc phthalocyanide (purchased from Sinopharm Group), grind it thoroughly and add it to 500ml of tetrahydrofuran liquid (purchased from Sinopharm Group), heat in a magnetically stirred oil bath at 80°C to evaporate all the liquid, evaporate The obtained solids were mixed, then placed in a muffle furnace to raise the temperature to 300° C. at 5° C. / min, and calcined at a constant temperature for 2 hours to prepare a porous carbon-zinc-cobalt-supported zinc phthalocyanide heterojunction catalyst. Take 50 mg of this catalyst, 500 μL of deionized water, and 1000 μL of Nafion solution (purchased from DuPont) with a mass concentration...

Embodiment 3

[0041] Take 100g of zinc-cobalt imidazole framework (Zn / Co ZIF) (average diameter 500nm) and put it into a tube furnace, and raise the temperature to 600°C at 5°C / min in a mixed gas of nitrogen and hydrogen (nitrogen 50vol%+hydrogen 50vol%) , and heated at constant temperature for 3 hours to obtain a calcined product. The calcined product was mixed with 10g of zinc phthalocyanide (purchased from Sinopharm Group), fully ground and added to 5000ml of tetrahydrofuran liquid (purchased from Sinopharm Group), and heated at 80°C in a magnetically stirred oil bath to evaporate all the liquid. The obtained solids were mixed, then placed in a muffle furnace to raise the temperature to 300° C. at 5° C. / min, and calcined at a constant temperature for 2 hours to prepare a porous carbon-zinc-cobalt-supported zinc phthalocyanide heterojunction catalyst. Take 100 mg of this catalyst, 1000 μL of deionized water, and 2000 μL of Nafion solution (purchased from DuPont) with a mass concentration ...

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Abstract

The present invention relates to CO 2 The gas conversion and utilization technology aims to provide a carbon-zinc-cobalt-supported zinc phthalocyanide heterojunction catalyst for double-light reduction of CO 2 Methods. Including: porous carbon-zinc-cobalt-supported zinc phthalocyanide heterojunction catalyst as the coating material of the cathode electrode, TiO 2 The anode electrode is made of nanotubes; the dual-light reactor adopts a transparent cavity, and the cathode electrode and the anode electrode are respectively installed, and the middle is separated by a Nafion film; the anode electrode is irradiated by the 365nm quasi-monochromatic band light of the xenon lamp, and the cathode electrode is irradiated by the visible light of the xenon lamp; Add saturated NaCl aqueous solution, add saturated NaHCO in the cathode chamber 3 aqueous solution, the CO 2 into the cathode chamber for double photoreduction reaction; the liquid products in the cathode chamber include methanol, ethanol and propanol, and the gaseous products in the cathode chamber include H 2 、CH 4 and CO. The present invention improves the CO 2 The selectivity of the reduction to liquid alcohol products; the separation efficiency of photogenerated electron-holes is improved and their recombination is inhibited, so that the double photoreduction of CO 2 The overall conversion efficiency of the reaction was increased by 50%.

Description

technical field [0001] The present invention is about the greenhouse gas CO 2 conversion and utilization technology, especially involving carbon-zinc-cobalt-supported zinc phthalocyanide heterojunction catalysts for double-light reduction of CO 2 Methods. Background technique [0002] Using light energy to convert greenhouse gas CO under the action of a catalyst 2 The reduction to methanol, ethanol, formic acid, methane and other organic compounds is a hot research direction to alleviate the greenhouse effect and energy shortage at the same time. CO as a stable gas 2 Molecular bonds are difficult to break, and in recent years CO 2 The transformation and utilization of them has become a research hotspot. Catalytic reduction of CO using double light irradiation 2 with pure photocatalytic reduction of CO 2 Compared with the following advantages: (1) the water splitting reaction and CO 2 The reduction reaction is separated by the proton exchange membrane, which can effec...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C25B1/00C25B1/04C25B3/04C25B11/03C25B11/06C25B3/25
CPCC25B1/00C25B1/04C25B3/25C25B11/031C25B11/051C25B11/091Y02E60/36
Inventor 程军岑可法周俊虎刘建忠王智化张彦威杨卫娟周志军何勇
Owner ZHEJIANG UNIV
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