CN114318369A - Preparation method and application of MXene quantum dot supported phthalocyanine molecule composite catalyst - Google Patents
Preparation method and application of MXene quantum dot supported phthalocyanine molecule composite catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method and application of an MXene quantum dot supported phthalocyanine molecule composite catalyst. The method selects a novel two-dimensional material Ti3C2MXene is used as a precursor to synthesize MXene quantum dots, and the end groups of the MXene quantum dots are regulated and controlled by changing a nonmetal source used in grafting a functional group, namely a fluorine source, a nitrogen source and an oxygen source; and then the controllable synthesis step at room temperature is adopted to enable the metal phthalocyanine and the MXene quantum dots to complete secondary coordination to form the composite molecular catalyst, and the MXene quantum dot-loaded phthalocyanine molecular composite catalyst with adjustable catalytic activity has originality. The invention prepares a series of catalysts containing secondary coordination effect as a catalytic main body to be applied to the field of electrocatalytic reduction of carbon dioxide, and realizes the high-efficiency and directional conversion of the carbon dioxide.
Description
Technical Field
The invention relates to a preparation method of a metal phthalocyanine molecule and MXene quantum dot composite material and application thereof in the field of electrocatalysis. In particular to a method for adjusting the catalytic activity of a supported phthalocyanine molecular composite catalyst by changing the type or the number of functional groups grafted by MXene quantum dots and application thereof in the field of electrocatalytic reduction of carbon dioxide.
Background
Electrocatalytic processes are very important in the transition from fossil fuels to renewable energy sources. Therefore, there is a need, under theoretical guidance, to design electrocatalysts with high activity, high selectivity and high stability for a specific reaction pathway. Early research was focused primarily on polycrystalline single metal catalysts because of their simple structure, ease of handling, and ease of study. Other than chem. eng.j.2021,427,130980 nanostructured monometallic, ionically modified metallic, bimetallic and non-metallic materials are widely used in the field of electrocatalysis. Nanomaterials typically have surfaces with more low coordination sites and larger active surface areas than conventional materials, and thus exhibit different catalyst characteristics than conventional materials. [ Nat Commun.2021,12,3264]
The phthalocyanine is a macrocyclic conjugated complex with 18 pi electrons, and a pi electron conjugated macrocyclic system conforms to the Hutt's rule so as to have aromaticity, and the structure of the phthalocyanine is very similar to porphyrin widely existing in nature. However, unlike porphyrins which play an important role in the organism, phthalocyanine is a compound which is completely synthesized artificially. The phthalocyanine ring has 1 cavity, can contain metal elements such as iron, copper, cobalt, tin, nickel and the like, and is combined to generate metal phthalocyanine molecules. Monodisperse homogeneous molecular catalysts such as metal phthalocyanines have typical M-N values per se4The atomic structure has clear active sites, and is easy for mechanism research; in addition, the central metal structure has height adjustability. However, the single metal phthalocyanine molecule used as a catalytic main body in the electrocatalysis field still has the defects of poor selectivity, low stability and the like, and the wide application of the metal phthalocyanine molecule is limited. [ Energy environ. Sci.,2021,14,2349]
Similar to homogeneous catalysts, monatomic catalysts (SACs) have attracted extensive attention from researchers due to their high atom utilization, and excellent activity and selectivity for various catalytic reactions. The strong interaction between the individual metal atoms and the support, as well as the unsaturated coordination environment of the SACs, can significantly improve the electrocatalytic performance. However, most SACs are prepared by pyrolysis at high temperatures, resulting in an uncontrolled coordination environment; furthermore, the surface free energy of the single atoms is high, making them prone to cluster to form clusters, complicating the analysis of catalytic reaction pathways and mechanisms. [ Small.2021,17,2103705]
Based on the above research, a few documents report that metal phthalocyanine molecules are loaded on carbon-based nano materials, and the interaction between the carbon substrate and the metal phthalocyanine molecules is explored. Wang group studied the electrocatalytic reduction of CO by cobalt phthalocyanine and carbon nanotube composite2Is CH3Influence of OH, catalysis of CO by cobalt phthalocyanine/carbon nanotube composites2The generation of a large amount of CO causes the poisoning and inactivation of the central atom of the metal phthalocyanine, so that the activity of the catalyst is sharply reduced, and CH is generated3The amount of OH decreases. In addition, the composite catalyst has H at higher overpotential2Cannot be ignored due to H2The reduction of (a) results in a rapid decrease in the electron cloud density on the phthalocyanine, causing the overall structure of the phthalocyanine to change and fail, eventually leading to a decrease in catalytic activity with time. [ Nature 2019,575,639]The Shui group researches the electro-catalytic reduction of CO by the composite material of cobalt phthalocyanine and acetylene black2Being the effect of CO, further improvement of catalytic activity is limited due to the lack of interaction of anchored CoPc with the matrix. [ ACS appl. energy Mater.2021,4,1442]
Therefore, how to develop a method with controllable preparation method and simple process can realize precise control of the coordination environment of the metal phthalocyanine molecule and definite positioning of the active site of the composite material catalyst, further optimize the binding energy of the active center metal atom and the reaction intermediate, and realize the directional and efficient conversion of the reactant is an urgent problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for regulating and controlling the catalytic activity of a supported phthalocyanine molecule composite catalyst through the type or the quantity of functional groups grafted on a substrate and application of the method in the field of electrocatalytic reduction of carbon dioxide. The method selects novel two-dimensional materialTi3C2MXene is used as a precursor to synthesize MXene quantum dots, and the end groups of the MXene quantum dots are regulated and controlled by changing a nonmetal source used in grafting a functional group, namely a fluorine source, a nitrogen source and an oxygen source. And then the controllable synthesis step at room temperature is adopted to enable the metal phthalocyanine and the MXene quantum dots to complete secondary coordination to form the composite molecular catalyst, and the MXene quantum dot-loaded phthalocyanine molecular composite catalyst with adjustable catalytic activity has originality. The invention prepares a series of catalysts containing secondary coordination effect as a catalytic main body to be applied to the field of electrocatalytic reduction of carbon dioxide, and realizes the high-efficiency and directional conversion of the carbon dioxide.
The technical scheme of the invention is as follows:
a preparation method of an MXene quantum dot supported phthalocyanine molecule composite catalyst comprises the following steps:
(1) mixing Ti3AlC2Immersing in hydrofluoric acid for 20-48h, taking out, centrifuging, and freeze drying to obtain Ti3C2-MXene; then adding the solution into a surface termination source solution, carrying out ultrasonic dispersion for 3-6h under an inert atmosphere, stirring for 2-48h at room temperature, and centrifuging to obtain a supernatant; dialyzing the supernatant for 3-6h, and collecting the dialysate to obtain Ti3C2-a-MXene quantum dot solution.
Wherein the concentration of the hydrofluoric acid is 35-45 wt%; the surface termination source is an F source, an O source or an N source, and the concentration range is 0.2-0.5 mol/L; adding 0.1-1.0 g of Ti into each 50mL of surface termination source solution3C2-MXene; adding 1-4 g Ti to 50-100 mL hydrofluoric acid3AlC2。
The Ti3C2The concentration of the-A-MXene quantum dot solution is 1.0-1.2 mg/mL.
The ultrasonic power is 100W-500W; the cut-off molecular weight of the dialysis bag is 500Da-3000 Da.
The inert gas is argon or nitrogen.
The Ti3C2In the-A-MXene quantum dots, A is a surface termination group, specifically-F, -OH or-NH2。
(2) Mixing Ti3C2Respectively adding the-A-MXene quantum dot solution and the metal phthalocyanine into an organic solvent, carrying out ultrasonic treatment for 1-4h, mixing the two solutions, and continuing to carry out ultrasonic dispersion for 0.2-1.0 h; then stirring for 20-24 hours at room temperature, finally centrifuging, washing, and freeze-drying to obtain the supported composite molecular catalyst CoPc-Ti3C2A QDs, namely MXene quantum dots load phthalocyanine molecular composite catalyst.
Wherein, each 30mL of the metal phthalocyanine solution contains 0.5-3 mg of metal phthalocyanine; adding 1-8mL of LTi into each 10mL of organic solvent3C2-a-MXene quantum dot solution; ti3C2The feeding mass ratio of the-A-MXene quantum dots to the metal phthalocyanine is 1-20: 1.
The freeze drying temperature is-40 ℃ to-60 ℃; the vacuum degree is 15-20 kPa.
The F source is sodium fluoride, lithium fluoride or ammonium fluoride; the O source is sodium hydroxide, potassium hydroxide or sodium carbonate; the N source is ammonia water or hydrazine hydrate.
The metal phthalocyanine is iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, copper phthalocyanine or tin phthalocyanine.
The metal phthalocyanine solution and Ti3C2The solvent added into the-A-MXene quantum dot solution is the same as the solvent added into the-A-MXene quantum dot solution, and is an organic solvent, specifically N-N, Dimethylformamide (DMF) or absolute ethyl alcohol.
The MXene quantum dot supported phthalocyanine molecule composite catalyst prepared by the method is used for electrocatalytic reduction of CO2A catalytic material.
The invention has the substantive characteristics that:
the supported molecular catalyst prepared by the invention is synthesized at room temperature, and the problems of complex and uncontrollable coordination effect between metal and a carrier caused by high-temperature carbonization are solved; the coordination environment of MXene quantum dots and central metal can be controlled by changing the functional groups at the edge of the carrier, and different functional groups form different secondary coordination, thereby being beneficial to the electrocatalytic reduction of CO2And (4) analyzing the mechanism of the reaction. The metal phthalocyanine molecules are adjustable, such as iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, copper phthalocyanine, tin phthalocyanine and the like; the MXene quantum dot end group functional group is adjustable, such as fluorine end group and hydroxyl groupAmino group, etc.; the quantity of the functional groups is adjustable, the catalyst is obtained by preparing MXene quantum dots with different sizes, and the MXene quantum dot supported phthalocyanine molecule composite catalyst with adjustable catalytic activity is pioneering. Therefore, the supported composite molecular catalyst prepared by the invention is a good catalytic main body.
The invention has the beneficial effects that:
(1) the invention provides a preparation method for regulating and controlling the catalytic activity of a composite molecular catalyst by changing the species or the number of functional groups grafted by MXene quantum dots;
(2) the supported phthalocyanine molecule composite catalyst obtained by the invention shows excellent electrochemical performance in the field of electrocatalytic reduction of carbon dioxide. Electrochemical reduction of CO by conventional cobalt phthalocyanine2The product is mainly CO, and the Faraday efficiency is only 76%. The composite catalyst obtained by the invention changes the adsorption of an intermediate in the electro-reduction process, greatly improves the selectivity of the catalyst, and can achieve the Faraday efficiency of CO of 100%. In addition, the composite molecular catalyst obtained by the invention has a secondary coordination effect, and the active site is definite, namely M-N4O1(M is a metal at the center of the metal phthalocyanine molecule). The electrochemical performance is excellent in the field of electrocatalytic reduction of carbon dioxide.
Drawings
FIG. 1 is a transmission electron microscope image of hydroxyl-rich MXene quantum dots prepared in example 1.
Fig. 2 is an X-ray photoelectron energy spectrum of the cobalt phthalocyanine supported hydroxyl-rich MXene quantum dot composite molecular catalyst prepared in example 4.
Fig. 3 is a test chart of the performance of the cobalt phthalocyanine supported hydroxyl-rich MXene quantum dot composite molecular catalyst for electrocatalytic reduction of carbon dioxide prepared in example 4.
FIG. 4 is a schematic structural diagram of the cobalt phthalocyanine supported hydroxyl-rich MXene quantum dot molecular catalyst prepared in examples 4-6 of the invention with secondary coordination effect. Wherein, the cobalt phthalocyanine can be replaced by iron phthalocyanine, nickel phthalocyanine, copper phthalocyanine, tin phthalocyanine and other molecules, and the hydroxyl-rich titanium carbide quantum dots can be replaced by titanium carbide quantum dot carriers with different functional groups.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
2g of Ti are weighed3AlC2Slowly added into 70ml of HF (40 wt%) within 15min, and stirred at 35 ℃ for 24h to etch the Al layer. Taking out and centrifuging, and washing the product by using deionized water until the pH value is more than or equal to 6. Collecting the precipitate, and freeze-drying for 24h (freeze-drying temperature-55 ℃, vacuum degree 15kPa) to obtain a sample Ti3C2 MXene。
500mg of Ti are weighed3C2MXene, dispersed in a flask containing 50mL of 0.5M NaOH solution, sonicated for 3h under argon, transferred to a water bath and stirred at room temperature for 48h under argon. Centrifuging the solution, collecting supernatant, dialyzing for 3h to neutrality (dialysis bag parameter is 1000Da), collecting dialysate to obtain hydroxyl-rich MXene quantum dot solution (Ti)3C2OH-MXene QDs) at a concentration of 1.0 mg/mL.
FIG. 1 is a transmission electron microscope image of hydroxyl-rich MXene quantum dots obtained in example 1. The average size of the prepared hydroxyl-rich MXene quantum dots is about 10nm, and no agglomeration is observed.
Examples 2 to 3
The other steps are the same as example 1, except that NaOH is replaced by NaF and NH respectively3·H2O, the subsequent steps are the same, and the obtained end groups are-F and-NH2MXene quantum dots (Ti)3C2-F-MXene QDs、Ti3C2-NH2-MXene QDs)。
Example 4
Weighing 4mL of the hydroxyl-rich titanium carbide quantum dot solution (containing 4mg of quantum dots) obtained in example 1 and dissolving in 10mL of DMF, weighing 4mg of cobalt phthalocyanine and dissolving in 60mL of DMF, respectively carrying out ultrasonic treatment on the two solutions for 1h, and then mixing and carrying out ultrasonic treatment for 0.5 h. Transferring the obtained solution to a flask, stirring for 20h at room temperature, collecting the solution in a centrifuge tube, washing for 3-5 times by using DMF (dimethyl formamide) and 3-5 times by using absolute ethyl alcohol, and freeze-drying (the freeze-drying temperature is-55 ℃, and the vacuum degree is 15kPa) to obtain the supported molecular catalyst CoPc-Ti3C2OH QDs。
Fig. 2 is an X-ray photoelectron energy spectrum of the cobalt phthalocyanine supported hydroxyl-rich MXene quantum dot composite molecular catalyst obtained in example 4. From the energy spectrum of O1s, it can be seen that TiO is excluded2、C-Ti-Ox、C-Ti-(OH)xAnd Al2O3In addition, Co-O coordination is also observed.
Fig. 3 is a test chart of the performance of the cobalt phthalocyanine supported hydroxyl-rich MXene quantum dot composite molecular catalyst for electrocatalytic reduction of carbon dioxide obtained in example 4. The composite catalyst has excellent electro-catalytic reduction of CO2The performance is high selectivity to CO, and the faradaic efficiency of CO generation is maintained above 90% in a wider potential range (600mV), and can reach 100% at most.
5mg of CoPc-Ti was weighed3C2OH QDs, and adding 475. mu.L of absolute ethyl alcohol, 475. mu.L of deionized water, and 50. mu.L of 0.5 wt.% Nafion solution, and ultrasonically dispersing for 1h to form a uniform dispersion. 50 μ L of the resulting dispersion was dropped on carbon paper (0.1 cm)-2) And (4) naturally drying at room temperature.
All electrochemical tests in the present invention were carried out in a conventional three-electrode cell using CHI760E electrochemical workstation with 0.1M KHCO electrolyte3And (3) solution. The conversion formula of the electrode potential and RHE is that E (vs. RHE) ═ E (vs. Ag/AgCl) +0.224V +0.0596 multiplied by pH. The testing process is carried out in CO2Saturated 0.1M KHCO3Electro-reduction of CO in electrolyte2Test, CoPc-Ti3C2The maximum Faraday efficiency of CO production by OH QDs can reach 100 percent.
FIG. 4 is a schematic structural diagram of the cobalt phthalocyanine supported MXene quantum dot molecular catalyst obtained in example 4-6 with secondary coordination effect. The phthalocyanine cobalt can be seen in the figure to coordinate with hydroxyl on MXene quantum dots through axial traction to form an asymmetric coordination structure.
Examples 5 to 6
The other steps are the same as example 4, except that the hydroxyl-rich MXene is usedQuantum dots (Ti)3C2-OH-MXene QDs) are replaced by terminal groups-F, -NH, respectively2MXene quantum dots (Ti)3C2-F-MXene QDs、Ti3C2-NH2-MXene QDs) to obtain the supported molecular catalyst CoPc-Ti with end groups of-F and-OH3C2F QDs、CoPc-Ti3C2NH2 QDs。
Examples 7 to 8
The other steps are the same as example 4 except that cobalt phthalocyanine and hydroxyl-rich MXene quantum dots (Ti)3C2-OH-MXene QDs) in a mass ratio of 1: 1 is replaced by 1: 5. 1: 10 (the mass of cobalt phthalocyanine is fixed to be 2mg), and the subsequent steps are the same to obtain the supported molecular catalyst CoPc-Ti3C2OH QDs-5、CoPc-Ti3C2OH QDs-10. The testing process is carried out in CO2Saturated 0.1M KHCO3Electro-reduction of CO in electrolyte2Test, CoPc-Ti3C2The maximum Faraday efficiency of CO production by OH QDs-5 can reach 75.2 percent, and the percentage of CoPc-Ti is3C2The maximum Faraday efficiency of CO production by OH QDs-10 can reach 65.4 percent.
Examples 9 to 10
The other steps are the same as the example 4 except that the metal phthalocyanine molecules are replaced by phthalocyanine cobalt and phthalocyanine tin and phthalocyanine iron, and the subsequent steps are the same to obtain the supported molecular catalyst SnPc-Ti3C2OH QDs、FePc-Ti3C2OH QDs. The testing process is carried out in CO2Saturated 0.1M KHCO3Electro-reduction of CO in electrolyte2Test, SnPc-Ti3C2The maximum Faraday efficiency of CO production from OH QDs is close to 40 percent, and the maximum Faraday efficiency is FePc-Ti3C2The maximum Faraday efficiency of CO production by OH QDs can reach 63.5 percent.
As can be seen from the above examples, the supported composite molecular catalyst CoPc-Ti prepared by the invention3C2The A QDs avoids the problem that the coordination effect between metal and a carrier is complex and uncontrollable due to high-temperature carbonization; the coordination environment of the MXene quantum dot and the central metal can be controlled by changing the functional group of the MXene quantum dot edge position,different functional groups will form different secondary coordinates; the high-density dispersion of single metal atoms on the MXene material is realized, and the number of metal active centers is obviously increased; reduction of CO in the presence of electricity2In-process CoPc-Ti with secondary coordination effect3C2The A QDs further optimizes the binding energy of active center metal atoms and reaction intermediates, and realizes the efficient directional conversion of reactants.
The invention is not the best known technology.
Claims (8)
1. A preparation method of an MXene quantum dot supported phthalocyanine molecule composite catalyst is characterized by comprising the following steps:
(1) mixing Ti3AlC2Immersing in hydrofluoric acid for 20-48h, taking out, centrifuging, and freeze drying to obtain Ti3C2-MXene; then adding the solution into a surface termination source solution, carrying out ultrasonic dispersion for 3-6h under an inert atmosphere, stirring for 2-48h at room temperature, and centrifuging to obtain a supernatant; dialyzing the supernatant for 3-6h, and collecting the dialysate to obtain Ti3C2-a-MXene quantum dot solution;
wherein the surface termination source is an F source, an O source or an N source, and the concentration range is 0.2-0.5 mol/L;
adding 0.1-1.0 g of Ti into each 50mL of surface termination source solution3C2-MXene; adding 1-4 g Ti to 50-100 mL hydrofluoric acid3AlC2；
The Ti3C2The concentration of the A-MXene quantum dot solution is 1.0-1.2 mg/mL;
the Ti3C2In the-A-MXene quantum dots, A is a surface termination group, specifically-F, -OH or-NH2；
(2) Mixing Ti3C2Respectively adding the-A-MXene quantum dot solution and the metal phthalocyanine into an organic solvent for ultrasonic treatment for 1-4 hours, mixing the two solutions, and continuing to perform ultrasonic dispersion for 0.2-1.0 hour; then stirring at room temperature for 20-24 hours, finally centrifuging, washing, and freeze-drying to obtain the supported composite molecular catalyst CoPc-Ti3C2A QDs, i.e. MXAn ene quantum dot supported phthalocyanine molecular composite catalyst;
wherein, Ti3C2The feeding mass ratio of the-A-MXene quantum dots to the metal phthalocyanine is 1-20: 1.
2. The preparation method of the MXene quantum dot supported phthalocyanine molecule composite catalyst according to claim 1, wherein the concentration of the hydrofluoric acid is 35-45 wt%; the inert gas is argon or nitrogen.
3. The preparation method of MXene quantum dot supported phthalocyanine molecule composite catalyst of claim 1, wherein dialysis bag cut-off molecular weight is 500Da-3000 Da.
4. The preparation method of MXene quantum dot supported phthalocyanine molecule composite catalyst according to claim 1, wherein the ultrasonic power in step (1) or (2) is 100W-500W; the freeze drying temperature is-40 ℃ to-60 ℃; the vacuum degree is 15-20 kPa.
5. The method for preparing the MXene quantum dot supported phthalocyanine molecule composite catalyst of claim 1, wherein the F source is sodium fluoride, lithium fluoride or ammonium fluoride; the O source is sodium hydroxide, potassium hydroxide or sodium carbonate; the N source is ammonia water or hydrazine hydrate.
6. The method for preparing MXene quantum dot supported phthalocyanine molecule composite catalyst of claim 1, wherein the metal phthalocyanine is iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, copper phthalocyanine or tin phthalocyanine.
7. The preparation method of the MXene quantum dot supported phthalocyanine molecule composite catalyst of claim 1, wherein each 30mL of the metal phthalocyanine solution contains 0.5-3 mg of metal phthalocyanine; adding 1-8mL of Ti into each 10mL of organic solvent3C2-a-MXene quantum dot solution; the metal phthalocyanine solution and Ti3C2The solvent added into the solution of the-A-MXene quantum dots is the same as the solvent added into the solution of the-A-MXene quantum dots, and the solvent is the same as the solvent added into the solution of the-A-MXene quantum dotsThe organic solvent is N-N, Dimethylformamide (DMF) or anhydrous ethanol.
8. The use of MXene quantum dot supported phthalocyanine molecular composite catalyst prepared by the method of claim 1 as electrocatalytic reduction CO2A catalytic material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883561A (en) * | 2022-04-18 | 2022-08-09 | 北京理工大学 | Two-dimensional transition metal monatomic catalyst and preparation method and application thereof |
| CN115999584A (en) * | 2022-12-16 | 2023-04-25 | 广州大学 | Carbon-based-sulfide heterogeneous point compound and preparation method and application thereof |
| CN117543032A (en) * | 2024-01-09 | 2024-02-09 | 北京师范大学 | Active functional group-containing MXene-loaded phthalocyanine iron catalyst, and preparation method and application thereof |
| CN117594809A (en) * | 2024-01-19 | 2024-02-23 | 北京师范大学 | Multilayer TiN/phthalocyanine iron composite material electrocatalyst, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018132937A1 (en) * | 2017-01-17 | 2018-07-26 | South University Of Science And Technology Of China | Use of metal phthalocyanine/nanocarbon hybrid catalysts for efficient electrochemical reduction of co2 |
| CN110404588A (en) * | 2019-08-20 | 2019-11-05 | 大连理工大学 | A kind of ultra-thin stratiform FeNi-LDH-FePc MXene bifunctional catalyst and preparation method |
| CN111763213A (en) * | 2020-06-01 | 2020-10-13 | 南方科技大学 | Metal phthalocyanine-MXene composite material, supercapacitor and preparation method of supercapacitor |
| CN112206830A (en) * | 2020-10-28 | 2021-01-12 | 苏州大学 | CuPc@Ti3C2TxMXene catalytic material, electrode and application in nitrate radical reduction |
| CN112264062A (en) * | 2020-10-28 | 2021-01-26 | 兰州交通大学 | Preparation and application of monatomic platinum catalyst based on MXene quantum dots |
-
2022
- 2022-01-07 CN CN202210024546.5A patent/CN114318369B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018132937A1 (en) * | 2017-01-17 | 2018-07-26 | South University Of Science And Technology Of China | Use of metal phthalocyanine/nanocarbon hybrid catalysts for efficient electrochemical reduction of co2 |
| CN110404588A (en) * | 2019-08-20 | 2019-11-05 | 大连理工大学 | A kind of ultra-thin stratiform FeNi-LDH-FePc MXene bifunctional catalyst and preparation method |
| CN111763213A (en) * | 2020-06-01 | 2020-10-13 | 南方科技大学 | Metal phthalocyanine-MXene composite material, supercapacitor and preparation method of supercapacitor |
| CN112206830A (en) * | 2020-10-28 | 2021-01-12 | 苏州大学 | CuPc@Ti3C2TxMXene catalytic material, electrode and application in nitrate radical reduction |
| CN112264062A (en) * | 2020-10-28 | 2021-01-26 | 兰州交通大学 | Preparation and application of monatomic platinum catalyst based on MXene quantum dots |
Non-Patent Citations (6)
| Title |
|---|
| ADEM SREEDHAR ET AL.: "Photocatalytic and electrocatalytic reduction of CO2 and N2 by Ti3C2 MXene supported composites for a cleaner environment: A review", 《JOURNAL OF CLEANER PRODUCTION》, vol. 328, pages 129647 * |
| 李子兰: "酞菁铁电子结构调制及其电催化氧还原性能研究", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》, pages 014 - 486 * |
| 王开林等: "铋酞菁的制备及电催化CO_2还原性能研究", 《化工技术与开发》 * |
| 王开林等: "铋酞菁的制备及电催化CO_2还原性能研究", 《化工技术与开发》, 15 March 2020 (2020-03-15) * |
| 魏文英等: "水溶性介质中CO_2电催化还原研究进展", 《化工进展》 * |
| 魏文英等: "水溶性介质中CO_2电催化还原研究进展", 《化工进展》, no. 02, 28 February 2007 (2007-02-28) * |
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| CN115999584A (en) * | 2022-12-16 | 2023-04-25 | 广州大学 | Carbon-based-sulfide heterogeneous point compound and preparation method and application thereof |
| CN115999584B (en) * | 2022-12-16 | 2024-08-06 | 广州大学 | Carbon-based-sulfide heterogeneous point compound and preparation method and application thereof |
| CN117543032A (en) * | 2024-01-09 | 2024-02-09 | 北京师范大学 | Active functional group-containing MXene-loaded phthalocyanine iron catalyst, and preparation method and application thereof |
| CN117543032B (en) * | 2024-01-09 | 2024-04-02 | 北京师范大学 | Active functional group-containing MXene-loaded phthalocyanine iron catalyst, and preparation method and application thereof |
| CN117594809A (en) * | 2024-01-19 | 2024-02-23 | 北京师范大学 | Multilayer TiN/phthalocyanine iron composite material electrocatalyst, preparation method and application thereof |
| CN117594809B (en) * | 2024-01-19 | 2024-04-16 | 北京师范大学 | Multilayer TiN/phthalocyanine iron composite material electrocatalyst, preparation method and application thereof |
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