CN114481167B - Preparation method and application of O-Ni SAC/MWCNTs composite catalyst - Google Patents
Preparation method and application of O-Ni SAC/MWCNTs composite catalyst Download PDFInfo
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Abstract
A preparation method and application of an O-Ni SAC/MWCNTs composite catalyst. The composite catalyst material is prepared by taking nickel acetylacetonate as a metal source, a carboxylated carbon nanotube as a carrier, sodium chloride and potassium chloride as a medium of molten salt, carbonizing at high temperature in an inert atmosphere, acidifying, washing with water, and oxidizing in an oxidizing acid environment. The composite catalyst synthesized in the molten salt environment has more exposed end positions and edge positions, is beneficial to anchoring and attaching more monoatomic atoms, and provides more active sites for subsequent catalytic reaction. The strategy of oxygen-containing functional group modification adopted by the invention promotes the efficient and selective generation of hydrogen peroxide by oxygen reduction. The prepared oxygen-containing functional diagram modified nickel monatomic supported multi-walled carbon nanotube material shows high catalytic activity in the reaction of efficiently producing hydrogen peroxide by oxygen reduction, and the concentration of the hydrogen peroxide generated after quantitative analysis can completely meet the requirements of industrial bleaching and disinfection.
Description
Technical Field
The invention belongs to the field of new materials, and relates to preparation of a novel nickel metal monatomic catalyst, namely, a monatomic catalyst material is synthesized by calcining on a carboxylated multi-walled carbon nanotube in a molten salt environment, and then O-Ni SAC/MWCNTs (SAC = monatomic catalyst, MWCNTs = carboxylated multi-walled carbon nanotube) is obtained by modifying an oxygen-containing functional group through carrying out oxidation treatment of oxyacid on the synthesized monatomic catalyst. The invention also relates to the use of the catalyst.
Background
Hydrogen peroxide is one of the most valuable chemicals and is attractive for both residential and industrial applications, such as surgical disinfection, water purification, industrial pulp bleaching, chemical synthesis and fuel cell technology. Hydrogen peroxide (H) 2 O 2 ) Is a widely used expensive chemical. One recent trend in hydrogen peroxide production is electrochemical reduction of oxygen, which is an environmentally friendly method of in situ generation of hydrogen peroxide. To realize efficient and practical hydrogen peroxide electrosynthesis, the design of the catalytic material must be carefully studied. The catalyst with high activity, high selectivity and high stability is the basis for efficiently producing the hydrogen peroxide.
Wang et al (nat. Mater.2020,19, 436-442) demonstrated that a single atom directs the ORR pathway from 2e with omni-directional control - Is routed to H 2 O 2 Instead of 4e - Pathway to H 2 And (O). A series of single atoms including Pd, fe, mn and Co are modified on carbon nanotubes, and in these catalysts, fe modified CNTs (Fe-CNTs) catalyze H 2 O 2 The best activity and selectivity are shown in the aspect of production. Under alkaline condition, the initial potential of the electrode is 0.822V 2 O 2 Selectivity greater than 95%, by coordinative substitution of adjacent O with N, 2e can be achieved - ORR radial 4e - The pathway moves. The optimized Co-N-C catalyst not only shows high selectivity in N-doped graphene, but also generates H in alkaline electrolyte 2 O 2 The kinetic current of (2.8 mA cm) -2 The mass activity is 155A g -1 (at 0.65V compared to RHE), the decay in activity in alkaline electrolyte was negligible.
The Qiao group of subjects demonstrated (Angew. 2020,132, 9256-9261) that metal centers are not limited to traditional transition metals (e.g., fe, co, ni), but that other metal centers (e.g., sulfur-oxygen bidentate Mo SAC, mo-S4-C, and Mo-O3S-C) also exhibit high selectivity to 2e - And (5) ORR. Mo atom is considered to be 2e - Active source of pathway, local atom Environment pair 2e - High activity and high selection of pathwaysThe selectivity contributes.
Chang Hyuck Choi et al (nat. Comm.2020,7 2 O 2 The selectivity is up to 96%. The catalyst has both a high sulfur content (17 wt.% S) and a unique carbon structure (i.e., highly tortuous three-dimensional graphene nanoribbon network) that can stabilize relatively high platinum loadings (5 wt.%) in the form of highly dispersed species including atoms in isolated positions. In the oxygen reduction reaction, the catalyst does not follow the traditional four electron path to generate H 2 O, but rather selectively produces H even over an extended period of time 2 O 2 Without a significant decrease in activity. The process is therefore for preparing the important fine chemical H 2 O 2 Provides a potential promising route and also provides an opportunity to regulate the selectivity of other electrochemical reactions over various metal catalysts.
As described above, the carbon-based material has excellent stability, good electronic conductivity, and a large specific surface area, and thus is considered as an ideal electrocatalyst support. However, carbon materials exhibit inert characteristics and do not provide strong metal-support interactions. Therefore, the invention uses carboxylated carbon nanotubes as a carrier, uses nickel acetylacetonate as a metal source, calcines the obtained catalyst containing monatomic nickel in the environment of molten salt, and treats the obtained catalyst in the environment of oxidizing acid to prepare the nickel-based monatomic catalyst with oxygen modification, and the nickel-based monatomic catalyst shows high catalytic activity when used in the reaction for preparing hydrogen peroxide by oxygen reduction.
Disclosure of Invention
The invention aims to obtain the O-Ni SAC/MWCNTs composite catalyst material by taking nickel acetylacetonate as a metal source, a carboxylated carbon nanotube as a carrier, sodium chloride and potassium chloride as a medium of molten salt, carbonizing at high temperature in an inert atmosphere, washing with acidified water, and oxidizing in an oxidizing acid environment.
The technical scheme of the invention is as follows:
a preparation method of a nickel monoatomic supported multi-wall carbon nanotube composite catalyst modified by oxygen-containing functional groups comprises the following steps:
in the O-Ni SAC/MWCNTs composite catalyst material, nickel acetylacetonate is used as a metal source, a carboxylated carbon nanotube is used as a carrier, sodium chloride and potassium chloride are used as molten salt media, high-temperature carbonization is performed in an inert atmosphere, acid washing and oxidizing acid acidification treatment are performed to obtain the O-Ni SAC/MWCNTs composite catalyst, wherein SAC is a single-atom catalyst, and MWCNTs are carboxylated multi-wall carbon nanotubes.
In the oxygen-containing functional group modified nickel monoatomic supported multi-wall carbon nanotube composite catalyst, the mass fraction of carbon is 85-95%; the mass fraction of oxygen is: 5 to 10 percent; the mass fraction of the nickel is 0.5-2%.
Preparing a nickel monatomic supported multi-walled carbon nanotube catalyst material;
fully ball-milling a solid mixture of nickel acetylacetonate, a multi-walled carbon nanotube, potassium chloride and sodium chloride to uniformly mix the mixture; transferring the uniformly mixed solid into a quartz boat, transferring the quartz boat into a tube furnace for calcining, taking out a sample after the sample in the tube furnace is naturally cooled to room temperature, and grinding, acid washing, suction filtering and vacuum drying the sample to obtain a multi-walled carbon nanotube catalyst Ni SAC/MWCNTs supported by a nickel monoatomic atom;
wherein, nickel acetylacetonate: multi-walled carbon nanotubes: potassium chloride: the mass ratio of sodium chloride is 1;
the calcination temperature is 800-1000 ℃, the calcination time is 1-3 h, and the heating rate is 2-5 ℃/min;
step (2), preparing a nickel monoatomic supported multi-walled carbon nanotube composite catalyst modified by oxygen-containing functional groups;
heating and refluxing the Ni SAC/MWCNTs obtained in the step (1) in concentrated nitric acid with the concentration of 18mol/L, stopping heating after a certain time, naturally cooling to room temperature, centrifugally washing a sample until the sample is neutral, drying in vacuum, and recovering the sample to obtain the oxygen-containing functional group modified nickel monoatomic supported multiwalled carbon nanotube composite catalyst O-Ni SAC/MWCNTs;
wherein the reflux temperature is 60-90 ℃, and the reflux time is 12-72h.
An application of a nickel monoatomic-supported multi-walled carbon nanotube composite catalyst material modified by oxygen-containing functional groups in the production of hydrogen peroxide by electrocatalytic oxygen reduction,
the method is characterized in that the activity test and the quantitative test of the catalyst are carried out on a rotating ring disk electrode connected with an electrochemical workstation and in an H-shaped electrolytic cell connected with the electrochemical workstation, and the method specifically comprises the following steps:
step (1), preparation of catalyst slurry solution: adding the oxygen-containing functional group modified nickel monatomic supported multi-walled carbon nanotube composite catalyst to a mixed solution of isopropanol, water and 5wt% Naifion solution to prepare a uniform solution; wherein the volume ratio of isopropanol, water and 5wt% Naifion aqueous solution is 36:2:1, the concentration of the obtained catalyst is 1.5-2.5mg/mL;
and (2) testing the activity of hydrogen peroxide generated by electrochemical oxygen reduction: dripping the solution obtained in the step (1) on a ring disk electrode, drying to form a uniform film, connecting the uniform film to a rotary electrode rod, testing the activity of the catalyst by taking 1M KOH as electrolyte, ag/AgCl as a reference electrode and a graphite rod electrode as a counter electrode, and calculating H 2 O 2 Selectivity and electron transfer number of (a);
step (3) of generating H 2 O 2 The quantitative test of (2): in an H-type electrolytic cell, 1M KOH is used as electrolyte, ag/AgCl is used as a reference electrode, a graphite rod electrode is used as a counter electrode to test the activity of the catalyst, a constant current method is adopted, sampling is carried out for a certain time, and the yield of the catalyst is quantified by an ultraviolet visible absorption spectrophotometer for titration of a cerium sulfate solution.
The amount of catalyst dripped on the ring disk electrode in the step (2) is 18.18-50.50 mu g/cm 2 。
The current of the constant current test in the step (3) is 20-50mA.
The invention has the beneficial effects that: firstly, the monatomic nickel-supported multi-walled carbon nanotube material synthesized in the molten salt environment used by the method has more exposed end positions and edge positions, is beneficial to anchoring and attaching more monatomics, and provides more active sites for subsequent catalytic reaction. Second, the oxygen-containing functional group modification strategy employed in the present invention promotes efficient and selective hydrogen peroxide generation by oxygen reduction. Thirdly, the oxygen functional diagram modified nickel monoatomic supported multi-walled carbon nanotube (O-Ni SAC/MWCNTs) material prepared by the invention shows high catalytic activity in the reaction of efficiently producing hydrogen peroxide by oxygen reduction, and the concentration of the hydrogen peroxide generated after quantitative analysis can completely meet the requirements of industrial bleaching and disinfection.
Drawings
FIG. 1 is a scanning electron microscope photograph of an O-Ni SAC/MWCNTs composite catalyst, wherein it can be seen that the O-Ni SAC/MWCNTs composite catalyst material exhibits the morphological features of the carbon nanotubes being cut, exposing more end sites and edge sites, and the diameter of the material is about 40-60nm. Wherein, the magnification of the electron microscope is 45 ten thousand times, and the ruler is 200nm.
FIG. 2 is an XRD powder diffraction pattern of the MWCNTs and the O-Ni SAC/MWCNTs composite catalyst, and compares the XRD pattern (dotted line) of the O-Ni SAC/MWCNTs composite catalyst after loading monoatomic Ni with the XRD pattern (solid line) of the MWCNTs, wherein the XRD patterns of the O-Ni SAC/MWCNTs composite catalyst are basically consistent, no diffraction characteristic peak of nickel particles and nickel clusters is detected, and the metal nickel in the O-Ni SAC/MWCNTs composite catalyst is dispersed on a catalyst carrier in an atomic level dispersion mode.
FIG. 3 is a diagram showing the activity of O-Ni SAC/MWCNTs composite catalyst in electrochemical oxygen reduction for producing hydrogen peroxide. Wherein the dots represent the selectivity of the hydrogen peroxide, the catalyst maintains high selectivity (90%) of the hydrogen peroxide under a wide voltage window (0.2-0.7V vs RHE), and the catalyst has strong capability of efficiently producing the hydrogen peroxide by oxygen reduction. The curve represents the calculated electron transfer number for the catalyst, which is closer to 2e - The process can reflect that the catalyst has good catalytic oxygen electrochemistry 2e - Pathway reduction of the ability to produce hydrogen peroxide.
FIG. 4 is a graph of voltage change with time under constant current for hydrogen peroxide production by electrochemical oxygen reduction of O-Ni SAC/MWCNTs composite catalyst, sampling and titration analysis are carried out at a certain time, and the result shows that the concentration of hydrogen peroxide generated by the catalyst reaches about 3000mg/L and the voltage is maintained at 1.8V. This concentration of hydrogen peroxide is fully satisfactory for industrial bleaching and disinfection applications.
Detailed Description
The present invention is further illustrated by the following examples. The materials to which the present invention relates are not limited to the expressions in the following examples.
Example 1
Respectively adding nickel acetylacetonate, multi-walled carbon nanotubes, potassium chloride and sodium chloride solid into a ball milling tank, adding a proper amount of ball milling beads, and fully ball milling. The three substances are respectively as follows: nickel acetylacetonate 90mg: 135mg of multi-walled carbon nanotube: potassium chloride 4.68g: the amount of sodium chloride was 4.68g.
Calcining the mixed solid in an inert atmosphere tube furnace at 800 ℃, keeping the temperature for 2 hours, naturally cooling to room temperature at the heating rate of 5 ℃/min, fully pickling the obtained material with 10% hydrochloric acid solution at 80 ℃, fully washing the cooled material with distilled water, and drying the sample in vacuum for later use.
Comparative example 1
Respectively adding nickel acetylacetonate and multi-walled carbon nanotube solid into a ball milling tank, adding a proper amount of ball milling beads, and fully ball milling. The mass of the substances is respectively as follows: nickel acetylacetonate 90mg: 135mg of multi-wall carbon nano-tube.
Calcining the mixed solid in an inert atmosphere tube furnace at 800 ℃, preserving heat for 2 hours, naturally cooling to room temperature at the heating speed of 5 ℃/min, fully pickling the obtained material with 10% hydrochloric acid solution at 80 ℃, fully washing the material with distilled water after cooling, and drying the sample in vacuum for later use.
Comparative example 2
Respectively adding the multi-walled carbon nano tube, potassium chloride and sodium chloride solids into a ball milling tank, adding a proper amount of ball milling beads, and fully ball milling. The three substances are respectively as follows: 135mg of multi-walled carbon nanotube: potassium chloride 4.68g: the amount of sodium chloride was 4.68g.
Calcining the mixed solid in an inert atmosphere tube furnace at 800 ℃, keeping the temperature for 2 hours, naturally cooling to room temperature at the heating rate of 5 ℃/min, fully pickling the obtained material with 10% hydrochloric acid solution at 80 ℃, fully washing the cooled material with distilled water, and drying the sample in vacuum. The samples were tested directly without any further treatment.
To sum up, in example 1, potassium chloride and sodium chloride are used as a molten salt system to successfully synthesize the monatomic nickel-supported multi-walled carbon nanotube catalyst material, so that the constraint effect of the molten salt environment on the carbon material and the metal precursor is fully exerted, and the formation and anchoring of metal monatomic are facilitated. In contrast, comparative example 1 is a metallic nickel supported multi-walled carbon nanotube material synthesized without the participation of potassium chloride and sodium chloride, i.e., without a molten salt. The catalyst material formed by the scheme is a composite catalyst of single atom and metal cluster, metal nano particle heterozygosis, the types and the proportion of the several morphologies are difficult to control, and the source of the active center of the catalyst is difficult to identify. Comparative example 2 is the activity and selectivity of the catalyst material without metal precursors added for the calcination treatment of multi-walled carbon nanotubes in the presence of potassium chloride and sodium chloride, i.e. in a molten salt environment system, compared to the catalyst material without the presence of metal active sites.
Example 2
Putting 0.1g of the prepared Ni SAC/MWCNTs catalyst material into a three-neck flask, adding 100mL of concentrated nitric acid (18 mol/L), heating and refluxing at 80 ℃ for 24 hours, naturally cooling the solution to room temperature, centrifuging and washing the sample until the sample is neutral, drying in vacuum to obtain the O-Ni SAC/MWCNTs composite catalyst, and recovering the sample. The morphology results are shown in figure 1, and the XRD structure information is shown in figure 2.
Comparative example 3
Putting 0.1g of the prepared Ni SAC/MWCNTs catalyst material into a three-neck flask, adding 100mL of concentrated nitric acid (18 mol/L), refluxing at room temperature for 24 hours, naturally cooling the solution to room temperature, centrifugally washing the sample until the solution is neutral, drying in vacuum to obtain the O-Ni SAC/MWCNTs composite catalyst, and recovering the sample.
Comparative example 4
Putting 0.1g of the prepared Ni SAC/MWCNTs catalyst material into a three-neck flask, adding 100mL of concentrated nitric acid (18 mol/L), heating and refluxing for 12 hours at 80 ℃, naturally cooling the solution to room temperature, centrifuging and washing the sample until the sample is neutral, drying in vacuum to obtain the O-Ni SAC/MWCNTs composite catalyst, and recovering the sample.
Comparative example 5
Putting 0.1g of the prepared Ni SAC/MWCNTs catalyst material into a three-neck flask, adding 100mL of concentrated nitric acid (18 mol/L), heating and refluxing at 80 ℃ for 48 hours, naturally cooling the solution to room temperature, centrifuging and washing the sample until the sample is neutral, drying in vacuum to obtain the O-Ni SAC/MWCNTs composite catalyst, and recovering the sample.
In summary, example 2 is a modification procedure of oxygen containing functional groups based on a synthesized monatomic nickel supported multi-walled carbon nanotube (Ni SAC/MWCNTs) catalyst material, in contrast to example 1, which is a catalyst material without modification of oxygen containing functional groups. The carbon around the single atom is modified by the oxygen-containing functional group, so that the synergistic effect of the single atom position and the oxygen-containing functional group position is greatly promoted, and the activity of the catalyst is promoted to be improved. In contrast, the experimental control was performed for the process of modifying the oxygen-containing functional group, and comparative example 3 was a process of oxidizing the catalyst performed at room temperature, and the oxidation treatment temperature was low and the oxidation treatment degree of the material was insufficient. Comparative example 4 was heated at 80 ℃ under reflux for 12 hours, and the oxidation time was shorter than that of example 2, and the material was less oxidized and had a lower number of oxygen-containing functional groups. Comparative example 5, which is a heating reflux at 80 ℃ for 48 hours, has a longer oxidation time than example 2 and a higher degree of oxidation of the material, wherein the number of oxygen-containing functional groups is not much different from example 2, shows that the limit of the number of oxygen-containing functional groups that can be accommodated in the material itself has been reached by heating reflux at 80 ℃ for 24 hours, and that continuing to increase the oxidation time does not have a great influence on the number of oxygen-containing functional groups on the catalyst.
The O-Ni SAC/MWCNTs composite catalyst material shows very high hydrogen peroxide selectivity in the reaction for preparing hydrogen peroxide by oxygen reduction. The electrolytic solution consisted of 200ml,1m KOH solution, a suitable amount of catalyst slurry was applied dropwise to a rotating ring disk electrode head connected to an electrochemical workstation as a working electrode, a carbon rod was used as a counter electrode, and an Ag/AgCl electrode was used as a reference electrode, and the electrochemical test maintained the selectivity of hydrogen peroxide at about 90% over a wide potential range, and the electron transfer number was closer to that of two electron paths to generate hydrogen peroxide, the results of which are shown in fig. 3. The ability of the catalyst to produce hydrogen peroxide was quantitatively analyzed by constant current testing, spot sample titration analysis, and the results are shown in fig. 4.
Claims (4)
1. A preparation method of a nickel monoatomic supported multi-wall carbon nanotube composite catalyst modified by oxygen-containing functional groups is characterized by comprising the following steps:
preparing a nickel monatomic supported multi-walled carbon nanotube catalyst material;
fully ball-milling a solid mixture of nickel acetylacetonate, a multi-walled carbon nanotube, potassium chloride and sodium chloride to uniformly mix the mixture; transferring the uniformly mixed solid into a quartz boat, transferring the quartz boat into a tube furnace for calcining, taking out a sample after the sample in the tube furnace is naturally cooled to room temperature, and grinding, acid washing, suction filtering and vacuum drying the sample to obtain a multi-walled carbon nanotube catalyst Ni SAC/MWCNTs supported by nickel monatomic atoms;
wherein, nickel acetylacetonate: multi-walled carbon nanotubes: potassium chloride: the mass ratio of the sodium chloride is 1; calcination temperature of 800 o C-1000 o C, calcining for 1 to 3h at a temperature rise speed of 2 to 5 ℃/min;
step (2), preparing a nickel monoatomic supported multi-walled carbon nanotube composite catalyst modified by oxygen-containing functional groups;
heating and refluxing the Ni SAC/MWCNTs obtained in the step (1) in concentrated nitric acid with the concentration of 18mol/L, stopping heating after a certain time, naturally cooling to room temperature, centrifugally washing a sample until the sample is neutral, drying in vacuum, and recovering the sample to obtain the oxygen-containing functional group modified nickel monoatomic supported multiwalled carbon nanotube composite catalyst O-Ni SAC/MWCNTs;
wherein the reflux temperature is 60-90 deg.C o C, refluxing for 24-48h.
2. The application of the oxygen-containing functional group modified nickel monoatomic supported multi-walled carbon nanotube composite catalyst material prepared by the method of claim 1 in the production of hydrogen peroxide by electrocatalytic oxygen reduction,
the method is characterized in that the activity test and the quantitative test of the catalyst are carried out on a rotating ring disk electrode connected with an electrochemical workstation and in an H-shaped electrolytic cell connected with the electrochemical workstation, and the method specifically comprises the following steps:
step (1), preparation of catalyst slurry solution: adding the oxygen-containing functional group modified nickel monoatomic supported multi-walled carbon nanotube composite catalyst into a mixed solution of isopropanol, water and 5wt% Naifion solution to prepare a uniform solution; wherein the volume ratio of isopropanol, water and 5wt% Naifion aqueous solution is 36:2:1, the concentration of the obtained catalyst is 1.5-2.5mg/mL;
and (2) testing the activity of hydrogen peroxide generated by electrochemical oxygen reduction: dripping the solution obtained in the step (1) on a ring disk electrode, drying to form a uniform film, connecting the uniform film to a rotary electrode rod, testing the activity of the catalyst by taking 1M KOH as electrolyte, ag/AgCl as a reference electrode and a graphite rod electrode as a counter electrode, and calculating H 2 O 2 Selectivity and electron transfer number of (a);
step (3) of generating H 2 O 2 The quantitative test of (2): in an H-type electrolytic cell, 1M KOH is used as electrolyte, ag/AgCl is used as a reference electrode, a graphite rod electrode is used as a counter electrode to test the activity of the catalyst, a constant current method is adopted, sampling is carried out for a certain time, and the yield of the catalyst is quantified by an ultraviolet visible absorption spectrophotometer for titration of a cerium sulfate solution.
3. The use according to claim 2, wherein the amount of catalyst dropped on the ring disk electrode in step (2) is 18.18 to 50.50 μ g/cm 2 。
4. Use according to claim 2 or 3, wherein the galvanostatic test in step (3) has a current of 20 to 50mA.
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