CN110248731B - Metal-free catalysts derived from waste biomass for oxygen reduction reactions - Google Patents
Metal-free catalysts derived from waste biomass for oxygen reduction reactions Download PDFInfo
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- CN110248731B CN110248731B CN201680091939.0A CN201680091939A CN110248731B CN 110248731 B CN110248731 B CN 110248731B CN 201680091939 A CN201680091939 A CN 201680091939A CN 110248731 B CN110248731 B CN 110248731B
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/082—Decomposition and pyrolysis
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A method for preparing a metal-free catalyst for an oxygen reduction reaction comprising the steps of: mixing waste biomass (solid or liquid) and catalyst together to form a homogeneous powder or slurry; performing fast catalytic carbonization by heating the homogeneous mixture to obtain a highly porous carbonaceous intermediate material; blending a carbonaceous intermediate with melamine to form a carbon structure; modifying the nitrogen-rich compound by heating the carbon structure; and doping nitrogen into the carbon structure. The resulting catalyst has a hierarchical porous carbon structure with relatively high nitrogen doping and no metal.
Description
Technical Field
The present invention relates to metal-free catalysts for oxygen reduction reactions, including methods of making the same.
Background
The development of alternative and sustainable energy sources has become an urgent task due to the worldwide use of non-renewable fossil fuels, which cause serious environmental pollution (e.g. greenhouse gases and consequent global warming). In this context, fuel cells with high energy density and sustainable characteristics are of great interest. However, the conversion efficiency of such fuel cells is typically limited at the cell cathode by the slow Oxygen Reduction Reaction (ORR) due to the high activation energy of the reaction. The activation energy can be reduced by means of a catalyst and the currently popular choice is a noble metal based catalyst, typically a platinum (Pt) based material. Unfortunately, noble metal-based catalysts suffer not only from poor stability under some fuel cell conditions, but also from poor methanol tolerance. In addition, noble metals are very expensive and rare. Based on one study by the U.S. department of energy, pt-based catalysts account for about 50% of the total cost of fuel cells. Therefore, it is important to develop an inexpensive catalyst with high ORR efficiency, extremely strong methanol tolerance, and good mass production capability, but still remains a great challenge.
Carbonaceous materials are low cost and have high biocompatibility and electrocatalytic activity, which makes such metal-free catalysts good candidates for replacing platinum-based materials. In this context, carbon derived from waste biomass is of increasing interest due to its almost zero cost raw material and the reduction of the severe environmental burden when it is used. Generally, an excellent ORR catalyst should have a large specific surface area, suitable porosity (e.g., graded meso-microporous), and heteroatom doping (e.g., N-doping). However, because of the inherent properties of waste biomass (e.g., poor porosity, low N content), such carbons generally lack these important features without specific treatment. To circumvent this challenge, many methods have been proposed for improving biomass to overcome these difficulties.
Typical methods for circumventing the disadvantages in using biomass as metal-free catalyst are disclosed in Graglia et Al (ACS)Nano10, 2016, 4364-4371). Graglia discloses N-doped porous carbonaceous catalysts for oxygen reduction. The synthesis comprises four steps: 1) Extracting lignin from waste wood by hydrothermal treatment at 220 deg.C for 15h, dissolving in THF solvent and final vacuum drying, 2) passing HNO in anhydrous acetic acid 3 Nitrated lignin, 3) from H at 130 ℃ by Raney Nickel 2 Adding NO 2 Reduction of lignin to NH 2 Lignin, and 4) by ZnCl 2 KCl molten salt activation carbonization. Graglia et al report the introduction of NH into lignin 2 Groups and activation by molten salts are important to promote catalytic activity of the final carbonaceous product.
Zhang et al (Small 10, 2014, 3371-3378) describe the direct application of hydrothermal carbonization (180 ℃,10 h) to obtain waste grass based carbon of comparable Pt. After the hydrothermal reaction, the product was collected by centrifugation at 4500rmp for 15min. The product was then obtained by evaporating the solution at 70 ℃ for 6 h. Zhang et al found that the product was an N-doped carbon nanodot/nanoflake aggregate. The high content of pyridine N in carbon is essential for the high activity of the material.
Liu et al(Nanoscale 7, 2015, 6136-6142) developed one-step ZnCl 2 Activating the carbonization process to obtain the porous N-doped carbonaceous catalyst. The waste water calabash is used as a carbonaceous source. The carbon product is mainly doped with pyridine N and graphite N. The N source is derived from the original N-containing chemical in the water hyacinth. ZnCl 2 Plays a large role in hole generation. The product has comparable properties to Pt.
In another experiment, gao et al (Energy & Environmental Science 8, 2015, 221-229) carbonized amaranth waste directly to obtain high performance metal-free carbonaceous catalysts. No special treatment is used. Therefore, the process is very simple.
However, the above four typical methods are not generally accepted methods for converting spent biomass into superior ORR catalysts. Generally, high porosity and sufficient N-doping are two fundamental factors that determine the performance of metal-free ORR catalysts. But the chemical composition of the waste biomass varies between species. Some have a high content of N groups, and some do not. The porosity of the waste biomass also varies between the different types. Therefore, these four methods fail to obtain an excellent ORR catalyst by changing the variety of the waste biomass.
NH has been proposed 3 Activation is used as a method for successfully solving this problem (Energy & Environmental Science 7, 2014, 4095-4103. This method is common. During the activation, NH 3 Not only etching carbon to produce pores but also etching N 2 Covalently introduced into the carbon molecular structure. Despite the great improvement in ORR activity, this approach still suffers from some significant drawbacks as follows: a) NH (NH) 3 The use of gases is potentially hazardous, especially in large scale production; b) At NH 3 Prior to activation, time/energy consuming pre-treatment (e.g. hydrothermal process with freeze drying or high temperature carbonization) is required and C) the C-conversion efficiency of the waste biomass is relatively low, which does not meet the requirements for efficient resource recovery.
Summary of The Invention
The present invention not only achieves the universal conversion of waste biomass (solid or liquid) to superior ORR catalysts; but also has high conversion efficiency and is time efficient.
The present invention is a novel method for producing hierarchical porous carbon with high nitrogen doping and metal-free catalysts for ORR. The catalyst comprises mainly carbon and heteroatoms (e.g. nitrogen) but no metal. Such carbonaceous catalysts have a fractional porosity with a high content of micropores, which are prepared by a fast catalytic carbonization process using common waste biomass (solid or liquid) as precursor and then modified with nitrogen-rich compounds.
The key process of the invention comprises the following steps:
a) The mixture of waste biomass and catalyst, which has been placed in a bottle, is directly inserted into a vertical furnace that has been preheated to a specific temperature (c). This step is referred to as "fast catalytic carbonization" and results in a highly porous carbonaceous intermediate material. This sample is referred to as "CM Fast-acting toy -X ", whereinMRepresents the metal of the catalyst and X represents the temperature of the furnace. The carbon synthesized by the fast carbonization method without using a catalyst is labeled "Cfast-X", and
b) The carbonaceous intermediate is blended with melamine and the blend is heated to a specific temperature. This step is referred to as "nitrogen-rich compound modification". Nitrogen is then doped into the carbon structure. The sample is marked as "CM Fast-acting toy -X-melamine-Y ", wherein Y represents the activation temperature. For comparison, undoped graded porous carbon was treated without melamine and labeled "CM Quick-acting tool -X-Y”。
According to one embodiment of the invention, a hierarchical porous carbonaceous material is prepared by doping with high nitrogen by so-called fast catalytic carbonization (step 1, taking solid waste biomass as an example) and then modifying it with temperature-programmed heating (step 2). In step 1, carbonization is effected at a relatively low temperature (. Ltoreq.700 ℃). The mixture of raw material and catalyst is directly put into a relatively low temperature zone for fast carbonization. A vertical furnace is used in this step and a graded porous carbonaceous material is produced. The carbonaceous material is not the final product and is therefore referred to as an intermediate product. In step 2, the carbonaceous intermediate is further modified with a nitrogen-rich compound in a horizontal furnace at a relatively high temperature by temperature programming.
The invention can also be used to prepare graded porous nitrogen-doped carbons with excellent catalytic activity for Oxygen Reduction Reactions (ORR), which facilitate relevant electrochemical applications. The performance of carbon materials (metal free catalysts) reaches comparable levels of Pt.
The invention can also be used to prepare porous nitrogen-doped carbon with ORR catalytic activity by: using waste biomass (solid or liquid) as raw material, znCl 2 As a catalyst and using a nitrogen-rich compound such as a nitrogen dopant. Waste biomass is a common substance including pericarp, leaves, waste oils, and the like. Prior to carbonization, the solid waste biomass was dried at 105 ℃ making it brittle. The liquid waste biomass may be used as is. Compound ZnCl 2 Plays an important role in the creation of the hole. The waste biomass and ZnCl are ball-milled before carbonization 2 And mixed uniformly. The pores in the carbon exhibit a hierarchical character, with micropores predominating. The nitrogen-rich compound is used for preparing nitrogen-doped porous carbon. The nitrogen content of the carbon is greater than 3at%, with pyridine N and pyrrole N predominating. When used in ORR, the graded porous and nitrogen-doped carbon has high electrocatalytic activity.
Furthermore, the present invention can be used to prepare ORR active porous nitrogen doped carbon with high versatility, i.e. it can be used in a wide variety of biomass materials (solid or liquid). Fast catalytic carbonization produces hierarchical porous carbon, while modification with nitrogen-rich compounds introduces heteroatoms into the carbon structure. Based on this process, various types of common waste biomass are converted to high performance ORR catalysts without much concern about the impact of differences in waste biomass composition and microstructure on its performance in various applications.
According to the present invention, a porous carbon material can be produced with very high efficiency. At N 2 Under the protection of the stream, the homogeneous mixture of raw materials and catalyst was placed directly into the preheated tank. Carbonization is usually completed within 10min for solid waste biomass, and 1 hour for liquid waste biomass. Then taking out the carbonaceous intermediate to N 2 Filling tanks for rapid cooling(15 min). For solid waste biomass, the overall process takes less than 30min, and for liquid waste biomass 75min.
The present invention may also be used to prepare porous carbon materials in a continuous operation. Fast catalytic carbonization involves two actions: insertion and withdrawal. After the fast catalytic carbonization, the carbonaceous intermediate is directly taken out and then a new batch of fast carbonized material is formed by inserting a new batch of the mixture of raw material and catalyst directly into the tank.
Finally, it is an object of the present invention to provide a solution to reduce the environmental burden by converting waste biomass (solid or liquid) into valuable material. The conversion of the spent biomass to functional carbon material retains the carbon element and prevents its release into the natural environment.
The present invention relates to the following embodiments:
1. a method for preparing a metal-free catalyst for an oxygen reduction reaction comprising the steps of:
providing a homogeneous mixture by: (i) Mixing solid waste biomass and catalyst together to form a homogeneous powder, or (ii) mixing liquid waste biomass and catalyst together to form a homogeneous slurry;
performing fast catalytic carbonization by heating the homogeneous mixture in an inert atmosphere to obtain a porous carbonaceous intermediate material;
blending a carbonaceous intermediate material with melamine to form a carbon structure;
modifying the nitrogen-rich compound by heating the carbon structure; and
nitrogen is doped into the carbon structure.
2. The process of embodiment 1 wherein the catalyst is a metal chloride comprising one of zinc chloride, ferric chloride, aluminum chloride or mixtures thereof.
3. The process of embodiment 2 wherein the catalyst is ZnCl 2 And (3) powder.
4. The method of embodiment 1, wherein the mixing is performed as a ball mill.
5. The method of embodiment 1, wherein the step of mixing the solid biomass comprises the steps of:
washing the solid waste biomass with water to remove contaminants;
cutting the solid biomass into pieces;
drying the pieces in an oven until the biomass reaches a constant weight; and
the dried solid biomass was uniformly mixed with the metal chloride powder using a ball mill.
6. The method of embodiment 1, wherein the step of mixing the liquid biomass comprises: the liquid waste biomass without any pretreatment is directly and uniformly mixed with the metal chloride powder using a ball mill.
7. The method of embodiment 1, wherein the step of performing fast catalytic carbonization comprises the steps of:
placing the homogeneous mixture into a vertical bottle having nitrogen therein;
rapidly inserting the bottle into a vertical furnace that has been preheated to between 300 ℃ and 700 ℃ to form hierarchical porous carbon;
after a first period of time, pulling the bottle out of the vertical oven and inserting it into a water-filled container for rapid cooling;
after a second period of time, rinsing the carbon with an acid solution and water to remove and recover the metal catalyst; and
the carbon was dried until it had a constant weight.
8. The method of embodiment 7, wherein the vertical bottle is formed from one of quartz and titanium.
9. The process of embodiment 7, wherein the vertical oven is preheated to 400 ℃ for solid waste biomass and 650 ℃ for liquid waste biomass.
10. The process of embodiment 7, wherein the first time period is between 8 and 12 minutes, preferably 10 minutes for solid waste biomass and between 30-90 minutes, preferably 60 minutes for liquid waste biomass.
11. The method of embodiment 7, wherein the second period of time is between 12 and 18 minutes, preferably 15 minutes.
12. The process of embodiment 7, wherein the carbon is dried at between 60 ℃ and 80 ℃, preferably at 70 ℃.
13. The method of embodiment 7 wherein the acid solution is a solution of HCl.
14. The method of embodiment 1, wherein the waste biomass is an organic non-fossil material of biological origin, which is a byproduct or waste product.
15. The method of embodiment 14, wherein the material of biological origin is one of fruit peel, leaves, waste oil, wood or mixtures thereof.
16. The process of embodiment 1, carried out in an inert atmosphere.
17. The method of embodiment 16, wherein the inert atmosphere comprises N 2 And Ar.
18. The method of embodiment 1 wherein the step of doping with nitrogen involves the use of nitrogen-rich molecules to modify the carbon from fast catalytic carbonization.
19. The method of embodiment 18 wherein the nitrogen-rich molecule comprises urea, melamine, thiourea, dicyandiamide, or a mixture thereof.
20. The process of embodiment 1 wherein the nitrogen-rich compound modification is carried out at a temperature in the range of 800 to 1100 ℃.
21. A catalyst for electrochemical oxygen reduction reactions comprising or consisting of the structure: has a nitrogen-doped hierarchical porous carbon structure of at least 3at%, 13-90at%, 23-80at%, 33-70at%, and the catalyst does not contain a metal.
22. A catalyst according to embodiment 21, wherein the carbon has > 80% micropores of size less than 2 nm.
23. The catalyst of embodiment 21 wherein the carbon is 50-100% doped with pyridine nitrogen and pyrrole nitrogen.
The present invention may relate to the use of the above hierarchical porous carbon structure with nitrogen doping in a catalyst for electrochemical oxygen reduction reactions.
Brief Description of Drawings
The foregoing and other objects and advantages of the invention will be apparent from the following detailed description and the accompanying drawings, wherein like reference numerals represent like elements throughout the various views, and in which:
fig. 1 is a schematic illustration of the manufacturing process of hierarchical porous carbon and its N-doped product;
fig. 2A shows an SEM image of a carbon intermediate obtained by fast catalytic carbonization at 400 ℃; FIG. 2B shows the relationship between relative pressure and amount of adsorption for the carbon intermediate of FIG. 2A; fig. 2C shows the pore size distribution of the carbon intermediate of fig. 2A, and fig. 2D is a SEM image illustrating the nitrogen-doped carbon product after melamine modification; FIG. 2E shows the relationship between relative pressure and amount of adsorption for the nitrogen-doped carbon product of FIG. 2D; and figure 2F shows the pore size distribution of the nitrogen-doped carbon product of figure 2D;
fig. 3 shows the high resolution XPS spectra of the carbon product in the following order: c1s spectra of carbon intermediates prepared by fast catalytic carbonization at 400 ℃ (fig. 3A), 900 ℃ (fig. 3C), 1000 ℃ (fig. 3E) and 1100 ℃ (fig. 3G). Also shown are N1s XPS spectra of nitrogen-doped carbon products modified by melamine at 400 ℃ (fig. 3B), 900 ℃ (fig. 3D), 1000 ℃ (fig. 3F), and 1100 ℃ (fig. 3H);
FIG. 4A shows nitrogen-doped carbon product prepared by melamine modification at 1000 ℃ and commercial Pt/C in O 2 Linear Sweep Voltammetry (LSV) curves at 1600rpm rotation rate in saturated KOH solution, FIG. 4B shows various samples in O 2 LSV curve in saturated 0.1M KOH at 1600rpm rotation rate, FIG. 4C shows nitrogen-doped carbon product prepared by melamine modification at 1000 ℃ at different rotation rates at O 2 Saturated 0.1M KOH solution at 5mV s -1 And fig. 4D is a plot of the K-L at different potentials for the nitrogen-doped carbon product from fig. 4C prepared by melamine modification at 1000 ℃;
FIGS. 5A and 5B show nitrogen-doped carbon products prepared by commercial Pt/C catalysts and melamine modification at 1000 deg.C, in the absence of O 2 KOH solution of (3), O 2 Saturated KOH solution and O 2 Saturated KOH and MeOH in 50mVs -1 CV curve of lower ORR; FIG. 5C shows the production of nitrogen-doped carbon for the preparation by melamine modification at 1000 deg.CAnd without ZnCl 2 Nitrogen-doped carbon products prepared as catalysts in O 2 Measurement of the rotating Ring disk electrode at ORR at 1600rpm in saturated 0.1M KOH solution, with disk Current (I) d ) Shown in the lower half of the figure, and the loop current (I) r ) Shown in the upper half of the figure; FIG. 5D shows the nitrogen-doped carbon product produced by melamine modification at 1000 deg.C (solid line) and without the use of ZnCl at various potentials based on the corresponding RRDE data in FIG. 5C 2 The percentage of peroxide (black line) and the number of electron transfers (n) (blue line) of the nitrogen-doped carbon product of the catalyst preparation (dashed line);
FIG. 6 shows nitrogen-doped carbon product (FIG. 6A) and commercial Pt/C (FIG. 6B) at O prepared by melamine modification at 1000 deg.C 2 Saturated 0.1M KOH solution at 100mVs -1 1 st and 2000 th CV curves at the scanning rate of (a);
FIG. 7A shows CZN Fast-acting toy LSV curves for TrPC-400-melamine-1000 catalyst compared to conventional Pt/C catalyst, and FIG. 7B shows CZN Fast-acting toy CV curve of OPC-400-melamine-1000 catalyst compared to conventional Pt/C catalyst. CZn Fast-acting toy Tr in TrPC means leaf, CZN Fast-acting toy O in OPC means orange peel;
FIG. 8 shows the LSV curves for each of the following samples compared to conventional Pt/C: BP-1100-NH 3 -1000、CZn Fast-acting toy 400-Melamine-1000, BP-HT180-NH 3 800 and BPC-800-1h; and
fig. 9 shows a comparison of the capacitance of supercapacitors made with activated carbon according to the invention compared to commercially available supercapacitors;
fig. 10A shows an SEM image of porous carbon nanostructures derived from liquid waste biomass, and fig. 10B shows a TEM image.
Detailed Description
The invention described in detail below uses waste biomass (solid or liquid) to produce a catalytically active carbon material that is catalytically active for oxygen reduction reactions, which is currently achieved with precious metals, typically platinum (Pt). The main object of the present invention is to provide a low cost alternative to the very expensive precious metals. Another main object of the present invention is to reduce the environmental burden caused by the daily mass production of waste biomass.
In fact, the world produces 1400 billion metric tons of biomass annually from agriculture and many of them eventually become waste. The only common treatment of this biomass is open combustion, which results in severe air pollution. A common feature of waste biomass is that it contains a relatively high content of carbon (C), typically greater than 35wt%. This is close to the carbon content of the prototype biomass, glucose, which shows promise as a suitable carbon source. The present invention converts waste biomass into a functional carbonaceous material having excellent Oxygen Reduction Reaction (ORR) catalytic activity.
As a candidate for replacing Pt-based electrocatalysts in fuel cells, metal-free carbon materials have attracted the attention of many researchers due to their high conductivity, porous structure and excellent durability in alkaline solutions. However, the crude carbon material exhibits weak electrocatalytic activity. To enhance the electrocatalytic activity of common carbon materials, it appears that the electrical neutrality of the graphitic material is destroyed to produce a favorable O 2 Adsorbed charged sites can be effective. Introducing nitrogen (or P, B) atoms into graphene (or some other carbon nanomaterial) sp 2 The hybrid carbon skeleton proved to be highly effective in improving electrocatalytic performance. N-doped carbon materials have been studied very extensively by researchers throughout the world. Although some N-doped carbon electrocatalysts have comparable or even better electrocatalytic activity, and have better stability and fuel tolerance than Pt-based catalysts, these materials are typically based on carbon nanomaterials and nitrogen-containing organics, which are very expensive and limited by their raw materials. In addition, most current N doping methods are based on NH 3 An irritant gas, which can also cause environmental problems. When large-scale application is concerned, NH is used 3 As N 2 The N-doping method of the source is not suitable because of the difficulty of gas storage and transport. Based on the urgent need for highly active ORR catalysts, it is of great interest to develop low cost and efficient methods to obtain electrocatalysts from cheap raw materials and even waste.
A key step of the invention isMixing waste biomass with ZnCl 2 The catalyst was mixed uniformly. During the process of converting the waste biomass to obtain the electrocatalyst, the waste biomass is completely dried in an oven. The temperature of the oven is preferably set to greater than 100 ℃, which is the boiling point of water. It should be noted that the direct carbonization of the waste biomass retains its original microstructure, which in fact has a low content of porosity. Although treatment of the waste biomass is necessary, it is composed of many macromolecules and therefore it is generally not soluble in common solvents (e.g. water), which makes processing of the waste biomass relatively difficult. According to the invention, the waste biomass (solid or liquid) is treated with ZnCl by means of ball milling 2 And mixed uniformly. The milling process enables intimate contact between the raw material and the catalyst. It is preferred that the waste biomass be ball milled into fine powder particles prior to mixing with the catalyst, although it is also possible to mix the two substances directly without any pretreatment.
Another way to treat the waste biomass is to disperse it as a powder in ZnCl 2 In solution. This enables very good contact between the raw material and the catalyst. However, because of ZnCl during the drying process 2 Strongly interact with water molecules and waste biomass, so the drying process is very long. In fact, complete drying is almost impossible. Basically, the ball milling process is currently the best option for efficiently and uniformly mixing together the raw materials and the catalyst. Furthermore, ball milling is currently a mature industrial technology that meets the objectives of mass production. This ensures the possibility of scaling up the preparation of the reaction mixture. On the other hand, other metal chlorides (e.g. FeCl) 3 、MgCl 2 KCl and NaCl) can also cause the formation of porous carbon and are suitable for use in the present invention.
Another key step of the present invention is to rapidly carbonize the homogeneous mixture. Rapid heating is accomplished by placing the mixture directly into a furnace that has an inert atmosphere and has been preheated to a specific temperature. The high temperature enables the reaction mixture to be heated to the set point temperature very rapidly. Generally, the temperature is controlled within the range of 300-500 ℃ for solid waste biomass and-700 ℃ for liquid waste biomass. Too low a temperature will not allow initiation of carbonization, while too high a temperature may lead to partial combustion of the waste biomass, since an absolutely inert atmosphere is difficult to achieve. For example, when the carbonization is performed, the lid of the retort is raised and the bottle containing the reaction mixture is directly put therein. In this step, when the lid is raised, air around the furnace inevitably enters the tank, thereby diluting the inert gas in the tank and making possible combustion.
Generally, the decomposition of solid waste biomass begins at 250 ℃ and the weight loss of the biomass tends to stabilize when the temperature is raised to greater than 400 ℃. For the decomposition of solid waste biomass, this common and similar phenomenon is due to the similarity of the main constituents of the waste biomass, namely the C 2 、H 2 And O 2 And (3) element composition. ZnCl 2 Catalytic carbonization of waste biomass and ZnCl 2 Usually melting at-285 ℃. Molten ZnCl 2 The liquid may dissolve the waste biomass and its carbonaceous intermediates. The microstructure of the waste biomass is thus destroyed. The as-formed carbon (e.g. graphitized species) cannot be dissolved in molten ZnCl 2 Neutralize and precipitate. In this process, znCl 2 Causing the formation of porous carbon. The pore size of the porous carbon is in the range of 15nm to 50nm based on scanning electron microscopy. According to N 2 Pore size distribution of adsorption-desorption isotherms, the carbon having a hierarchical porosity and the predominant pore type being microporous. Such a pore configuration is beneficial for fast mass transfer. The rapid carbonization of each batch lasted 10 minutes. After that, the porous material was quickly taken out and put into the container with N 2 Filled boxes are used for rapid cooling. The cooling time was only 15 minutes. Essentially, the entire process takes only 25 minutes in total. Conventional prior art carbonization has three steps: gradual heating, isothermal heating, and cooling. These three steps typically require more than 5 hours per batch. This prior art is highly inconvenient to operate and cannot be applied to actual production. The big difference is that the operation with the present invention is very fast. After the carbon intermediate is removed from the canister, another bottle may be inserted for carbonization of the next batch. In fact, this process is almost continuous. This enables expansionLarge scale horizontal preparation, which cannot be achieved with the prior art. Also, for liquid waste biomass, the porous carbon nanostructures may be aided by ZnCl 2 Is easily obtained. Based on TEM images, the carbon nanostructures had uniform micropores.
ZnCl 2 It evaporates very easily at relatively high temperatures. Generally, when the temperature is greater than 750 ℃, its evaporation will become very intense. Therefore, most of ZnCl 2 Will escape from the furnace to the environment and cause serious environmental pollution. In the present invention, the very short carbonization time at temperatures well below 600 ℃ avoids this disadvantage of solid waste biomass. Note that for liquid waste biomass, the reaction system is sealed and free of ZnCl 2 Steam can escape.
The final key step of the invention is the modification of the porous carbon by nitrogen doping. Melamine may be used as a nitrogen source. The carbon intermediate obtained in the fast catalytic carbonization step has oxygen functional groups (e.g., -COOH, -COH, -CO). The amino group is a potential nucleophile at high temperatures and can react with porous carbon to achieve nitrogen doping. Melamine is a highly thermally stable compound. When the temperature is more than 345 c, it will be sublimated vigorously, but will be precipitated rapidly in a low temperature region. Melamine does not carbonize even when the temperature is greater than 800 ℃. Thus, melamine only acts as a nitrogen dopant and sublimed melamine can be easily recovered in the low temperature region. On the other hand, melamine can be decomposed into active N-containing species to react with chemically inert carbon to achieve N doping.
Conventional or prior art nitrogen doping methods are based on NH 3 The use of (1). In this process, NH 3 Plays an important role not only in nitrogen doping but also in pore generation. However, because of NH 3 Is highly irritating to humans and therefore potentially dangerous, which therefore limits the large scale production of carbon products. On the other hand, in NH 3 Prior to activation, a relatively long time/energy consuming pretreatment is required. For example, more than 10 hours of hydrothermal treatment are required for each batch, and several days of lyophilization are also required to avoid aggregation of the product. Furthermore, the C conversion efficiency of waste biomass is relatively low, which does not meet the resource recoveryAnd (6) harvesting.
A detailed process for preparing nitrogen-doped porous carbon is described below and generally illustrated in fig. 1.
The waste biomass (e.g., a mass of banana peel) is washed with water to remove the dirt. Then, it was cut into pieces and dried in an oven at 105 ℃ until it reached a constant weight. Mixing the dried biomass with ZnCl 2 The powders were uniformly mixed using a ball milling technique. Placing the uniform powder with N 2 In a vertical quartz bottle or a vertical titanium alloy bottle 10. The bottle is quickly inserted into a vertical furnace 12 which has been preheated to between 300 ℃ and 500 ℃ (for example 400 ℃) (step a). It is interesting to note that the volume of the dark yellow (from banana peel) mixture expands sharply after carbonization. After at least about 10 minutes, the bottle 10 is pulled out (step b) and inserted into a container 14 with water for rapid cooling. The cooling time is 15min. The entire carbonization process takes less than 30 minutes. Carbon washing with HCl acid solution and water to remove and recover ZnCl 2 (step c). The carbon is dried at between 60 ℃ and 80 ℃, preferably 70 ℃, until it has a constant weight. This may take about 6 hours.
The dried carbon is mixed with melamine (step d). The homogeneous mixture is placed in a porcelain boat, which is placed in a horizontal tube furnace 16. The mixture is heated to a specific temperature, for example between 800 ℃ and 1100 ℃. The whole doping process is carried out by N 2 And (5) atmosphere protection. After that, the temperature was allowed to naturally drop under ambient conditions.
As shown in the bottom of fig. 1, the fast catalytic carbonization according to the invention results in a volume expansion to the hierarchical porous carbon N-doped product. Fig. 2 has SEM images of carbon intermediates obtained by fast catalytic carbonization at 400 ℃ (fig. 2A) and nitrogen doped carbon products after melamine modification (fig. 2D). The scale bar for both images is 500nm. This illustrates the expansion. FIGS. 2B and 2E show N of the carbon intermediate and the nitrogen-doped carbon product, respectively 2 Adsorption-desorption isotherms. In addition, fig. 2C and 2F show the particle size distribution of the respective materials.
Fig. 3 shows the high resolution XPS spectra of the carbon product in the following order: a carbon intermediate prepared by fast catalytic carbonization at 400 ℃ (fig. 3A), 900 ℃ (fig. 3C), 1000 ℃ (fig. 3E), and 1100 ℃ (fig. 3G). Also shown are XPS spectra of nitrogen-doped carbon products modified with melamine at 400 ℃ (fig. 3B), 900 ℃ (fig. 3D), 1000 ℃ (fig. 3F), and 1100 ℃ (fig. 3H). The various lines in the figure represent specific C or N species, i.e., C1N1, C2N2, C3N3, C4N4 and N5, where C1 is sp2 hybridized graphitized carbon, C2 is sp 3C-C carbon, C3 is C-O or C-N, C4 is C = O; n1 is pyridine-N, N2 is an amine or imine, N3 is pyrrole N, N4 is quaternary N, and N5 is pyridine-N-oxide. The diagram of fig. 3 shows that the main components of the final carbon product comprise pyridine N and pyrrole N, which are active species for catalysis.
Various tests were run to confirm the gist of the present invention.
Example 1
Banana peel was used as the waste biomass in one test because it is a typical waste biomass material. The banana peel was washed with water to remove the dirt. It was then cut into pieces and dried in an oven at 105 ℃ until it reached a constant weight. Mixing the dried peel with ZnCl by ball milling 2 The powders were mixed uniformly and the skin: znCl 2 Is set to 1:5. milling time and milling rate were controlled at 30min and 500rpm, respectively. Placing the uniform powder therein with N 2 In the vertical quartz bottle 10. See fig. 1. The bottle is quickly inserted into the vertical furnace 12, the temperature of which has been raised to a specific value, for example 400 ℃. After a period of between 8 and 12 minutes, preferably 10 minutes, the bottle is pulled out and inserted into water for rapid cooling. The cooling time is between 12 and 18 minutes, preferably 15 minutes. Carbon washing with HCl-water solution to remove and recover ZnCl 2 . The carbon was dried in an oven at 70 ℃ until it had a constant weight.
The method comprises the following steps of 1:10 (carbon: melamine) weight ratio the dried carbon was mixed with melamine. The homogeneous mixture is placed in a porcelain boat, which is placed in a horizontal tube furnace 16. At 5 ℃ for min -1 And an isothermal time of 2 hours heats the mixture to a specific temperature. The whole doping process is carried out by N 2 And (5) atmosphere protection. After that, the temperature is allowed to naturally occur under ambient conditionsAnd decreases.
For different applications, melamine may be replaced or partially replaced by other chemicals, for example with 1:2 (carbon: KOH) weight ratio of KOH, urea, thiourea, dicyandiamide, mixtures thereof, and the like. Depending on the activation chemicals used, the product obtained in this step can be used as electrode material in supercapacitors and in oxygen reduction reactions.
Linear Sweep Voltammetry (LSV) tests were performed on the product of the invention and commercial Pt/C was used as reference material (figure 4). LSV is voltammetry, in which the current on a working electrode is measured while the potential or voltage between the working electrode and a reference electrode is linearly scanned in time. At the potential at which the species begins to be oxidized or reduced, the oxidation or reduction of the species is recorded as a peak or trough in the current signal.
As shown in FIG. 4A, for ORR, CZn Fast-acting toy 400-Melamine-1000 exhibits an initial potential and a reduction current similar to Pt/C, showing comparable electrocatalytic activity. This can be explained by the synergistic effect of relatively good conductivity, graded porosity and high N-doping levels. Other conditions were considered in the systematic experiments, including whether ZnCl was used or not 2 And the temperature of the fast catalytic carbonization and melamine modification. These tests show that CZN Fast-acting toy Optimum performance of 400-melamine-1000 (red line in fig. 4B). On the other hand, by reacting CZn Quick-acting tool 400-Melamine-1000 with CZN Fast-acting toy Comparison of-400-1000, the important role of N doping on catalytic activity was verified (fig. 4B). It should be noted that Zn is used in addition to the absence of the use of melamine to introduce N into the porous carbon Quick-acting tool Preparation of CZN under the same conditions as those of-400-Melamine-1000 (Red line) Fast-acting toy 400-1000 (green line). CZn Quick-acting tool The initial potential of-400-melamine-1000 is 82mV higher than that of CZN Fast-acting toy -an initial potential of 400-1000. The LSV curve in fig. 4C shows that the current density increases significantly when the spin rate is increased, which can be attributed to shorter diffusion paths. FIG. 4D is derived from FIG. 4C based on the Koutecky-Levich (K-L) equation, which is shown below:
whereinJ k Which is representative of the dynamic current density,J L ω represents the rotation rate (rpm) of the RDE for the limiting diffusion current density,Fis the Faraday constant, which is known as 96485 Cmol -1 ，D 0 Is a diffusion coefficient and O 2 The volume concentration is expressed asC 0 And υ is the dynamic viscosity of the electrolyte, and B can be obtained from the slope of the fit line.
On the basis of the K-L equation, n (number of electron transfer) can be calculated from B. Based on the analysis of the K-L diagram, the oxygen reduction process is mainly composed of four electron pathways (O) 2 +2H 2 O+4e - ＝4OH - ) Guidelines, which are consistent with the above analysis.
It should be noted that poor tolerance of noble metal catalysts to methanol is one of the biggest challenges for fuel cell applications. By measuring O in the presence of 3M methanol 2 CV curves run in saturated KOH to evaluate the resistance of the catalyst of the invention to methanol oxidation. As shown in fig. 5A, a pair of peaks (valleys) was found at 0.12V and 0.16V and could be attributed to the methanol oxidation reaction of the Pt/C catalyst. While in FIG. 5B, CZn Fast-acting toy Hardly any change was observed for-400-melamine-100 under methanol conditions and under normal conditions, indicating that the prepared samples have better methanol tolerance than the commercial Pt/C catalyst. In addition, in N 2 And O 2 CV curves tested in saturated KOH solutions indicate O over the potential range 2 Presence of reduction peak.
For further understanding by CZN Fast-acting toy Electron transfer route to oxygen-catalyzed reaction of 400-melamine-100, performing Rotating Ring Disk Electrode (RRDE) measurements and subsequent analysis of HO during oxygen reduction 2 - Is generated. Measuring the Ring Current and the disk Current to obtain the in-reactionHO in (1) 2 - Yield (fig. 5C).
CZn in 0.1M KOH Fast-acting toy 400-Melamine-1000 and C Fast-acting toy HO recorded in the potential range of-0.55V to-0.2V of 400-melamine-1000 2 - Are less than 20% and 50%, respectively, showing corresponding electron transfer numbers of 3.7 and 3.3 (FIG. 5D). CZn Fast-acting toy The results of the K-L diagram of-400-melamine-1000 agree well with the RRDE results, which confirm the CZn Fast-acting toy Near four electron transfer routes during the oxygen reduction process of 400-melamine-1000.
As shown in fig. 6A, CZn in cycle 1 Fast-acting toy The CV curve of-400-melamine-1000 is perfectly matched to the 2000 th cycle, indicating its excellent durability in alkaline solutions. The stability of Pt/C in 0.1M KOH was also evaluated to confirm CZn Fast-acting toy -400-melamine-1000 in fuel cells for long-term operation. In FIG. 6B, the CV curves of Pt/C at cycle 1 and 2000 are less consistent with each other, indicating a match with CZN Fast-acting toy Pt/C has relatively weak durability compared to 400-melamine-1000.
Example 2
The tests of the present invention were also performed using typical solid waste biomass other than banana peel. They include orange peels and leaves. The preparation procedure is similar to that described in example 1 (which uses banana peel). The generality of the invention was demonstrated here with orange peel and leafy biomass. As illustrated in fig. 7, the corresponding carbon material exhibited good catalytic activity, which is very close to that of commercial Pt/C catalysts. It should be noted that the preparation conditions for these carbon materials and CZN Fast-acting toy Exactly the same for-400-melamine-1000. Although the optimum carbonization conditions for these two raw materials are most likely to be different from each other due to their different compositions and microstructures, the identity performance analysis still strongly suggests the high effectiveness of the present process for the universal production of superior carbon materials from common solid waste biomass.
The present invention has broad application to different types of solid waste biomass, including fruit peels, leaves and wood.
Example 3
In addition to solid waste biomass, the process can also be used to convert liquid waste biomass into porous functional carbon materials. A typical procedure includes: 1mL of illegal cooking oil was mixed with 16g of ZnCl by uniformly and earth-milling at a speed of 300rpm for 10min 2 Mixing; placing the mixture into Al 2 O 3 In a crucible; placing the crucible in a crucible having N 2 A protected Ti alloy can; the jar was sealed and placed directly into an oven that had been preheated to a temperature of 650 ℃ for 1 hour. After that the tank is pulled directly out of the furnace and inserted into water for rapid cooling. The porous morphology of the carbonaceous product can be found in fig. 10. This carbonaceous product was modified with melamine using the same procedure as in example 1 to obtain N-doped porous carbon nanostructures.
Example 4
Example 4 is a comparative example, which applies the method of the present invention to prepare nitrogen doped porous carbon from waste biomass. NH 3 Used as a nitrogen source and pore producing agent. The procedures were exactly the same as those in examples 1 and 2. As illustrated in FIG. 8, with CZn Fast-acting toy Comparison of-400-Melamine-1000 (Red Curve), all of these samples (i.e., BP-1100-NH) 3 -1000、BP-HT180-NH 3 800 and BPC-800-1h and conventional Pt/C) showed slightly poor ORR catalytic performance. This fully demonstrates the superiority of the current process in making high performance metal-free ORR catalysts.
The resource recoverability of the present invention was investigated based on comparison of C conversion efficiency with other classical methods reported previously (table 1 below). Take the activation of the N-rich molecule as an example. As shown in table 1, the C conversion efficiency of the present invention was as high as 41.9%. However, without the use of a catalyst in the fast carbonization, the C conversion efficiency rapidly dropped to 17.2%. The C conversion efficiency of the previous process was also measured. This value is less than 31%. These results strongly demonstrate the excellent resource recyclability of the present invention. Here, the present invention has a great ability for mass production in consideration of manufacturing efficiency and C conversion efficiency.
TABLE 1
Comparison of the yield, C content and C conversion efficiency of the carbon product formed by the process of the present invention and the reported prior art process
| Method | M Finally, the product is processed /M Raw materials | C content (wt.%) | C conversion efficiency (%) |
| a Gradual heating&NH 3 Activation of | 0.033 | 55.4 | 4.2 |
| b Hydrothermal process&NH 3 Activation of | 0.127 | 61.6 | 17.9 |
| c Direct carbonization | 0.184 | 73.1 | 30.8 |
| d The current method does not use catalyst | 0.091 | 82.4 | 17.2 |
| Current methods | 0.204 | 89.7 | 41.9 |
a、b、c The sample preparation procedure was exactly the same as in the following article: (a) f. Pan, z. Cao, q. Zhao, h. Liang and j. Zhang, j. Power Sources, 2014, 272, 8-15, (b) p. Chen, l. -k. Wang, g. Wang, m. -r. Gao, j. Ge, w. -j. Yuan, y. -h. Shen, a. -j. Xie and s. -h. Yu, energy environ. Sci., 2014, 7, 4095-4103, and (c) s. Gao, k. G, h. Liu, x. Wei, m. Zhang, p. Wang and j. Wang, energy environ. Sci., 8, 221-229. Attention is paid to d : except that no ZnCl is added in the fast carbonization step 2 Except for the fact that the same conditions and procedures as in the current method were used.
The activated carbon prepared by melamine activation according to the present invention can be used for Oxygen Reduction Reaction (ORR), which is important in fuel cells. A common material used for ORR is the noble metal, pt, which is very expensive. As can be seen in fig. 4, the material of the present invention outperforms Pt.
Supercapacitors have important applications in electric vehicles. The activated carbon prepared by KOH activation according to the present invention can be used in supercapacitors. The performance was better than that of the commercial, as shown in fig. 9.
The invention uses a metal catalyst (e.g., znCl) 2 ) To improve the carbon conversion efficiency and the porosity of the carbon obtained in the carbonization step of the waste biomass. The process avoids the use of high doses of activating chemicals and improves the quality of the carbon product. However, unlike traditional metal catalysts, current catalysts are used for fast reactions at temperatures well below the boiling point of the catalystA pyrolysis technology. Therefore, the corrosion of the manufacturing equipment is low and the manufacturing efficiency is very high. Furthermore, the process can be carried out continuously, as compared with conventional processes.
While the invention has been particularly shown and described with reference to a preferred embodiment thereof, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (16)
1. A method for preparing a metal-free catalyst for an oxygen reduction reaction comprising the steps of:
providing a homogeneous mixture by: (i) Mixing together solid waste biomass and metal chlorides to form a homogeneous powder, or (ii) mixing together liquid waste biomass and metal chlorides to form a homogeneous slurry;
performing fast catalytic carbonization by heating the homogeneous mixture in an inert atmosphere to obtain a porous carbonaceous intermediate material;
blending the carbonaceous intermediate material with melamine to form a carbon structure;
modifying the nitrogen-rich compound by heating the carbon structure;
doping nitrogen into the carbon structure to obtain a metal-free catalyst;
wherein the step of fast catalytic carbonization comprises the steps of:
placing the homogeneous mixture into a vertical bottle having nitrogen therein;
rapidly inserting the bottle into a vertical furnace that has been preheated to between 300 ℃ and 700 ℃ to form hierarchical porous carbon;
after a first period of time, pulling the bottle out of the vertical oven and inserting it into a water-filled container for rapid cooling;
after a second period of time, rinsing the graded porous carbon with an acid solution and water to remove and recover metal chlorides; and
the washed hierarchical porous carbon is dried until it has a constant weight.
2. The method of claim 1, wherein the metal chloride comprises one of zinc chloride, ferric chloride, aluminum chloride, or mixtures thereof;
wherein the solid waste biomass and metal chlorides are mixed by ball milling;
wherein the step of mixing the solid waste biomass comprises the steps of:
washing the solid waste biomass with water to remove contaminants;
slicing the washed solid waste biomass;
drying the sheet in an oven until the biomass reaches a constant weight; and
uniformly mixing the dried solid waste biomass with metal chloride powder using a ball mill; and/or
Wherein the step of mixing the liquid waste biomass comprises: the liquid waste biomass without any pretreatment is directly and uniformly mixed with the metal chloride powder using a ball mill.
3. The process of claim 2, wherein the metal chloride is ZnCl 2 And (3) powder.
4. The method of claim 3, wherein the vertical bottle is formed from one of quartz and titanium;
wherein the vertical furnace is preheated to 400 ℃ for solid waste biomass and to 650 ℃ for liquid waste biomass;
wherein the first time period is between 8-12 minutes for solid waste biomass and between 30-90 minutes for liquid waste biomass;
wherein the second time period is between 12-18 minutes;
wherein the washed hierarchical porous carbon is dried between 60 ℃ and 80 ℃; and/or
Wherein the acid solution is a solution of HCl.
5. The method of claim 4, wherein the first period of time is 10 minutes for solid waste biomass.
6. The method of claim 4, wherein the first time period is 60 minutes for liquid waste biomass.
7. The method of claim 4, wherein the second period of time is 15 minutes.
8. The method of claim 4, wherein the washed hierarchical porous carbon is dried at 70 ℃.
9. The method of claim 1, wherein the waste biomass is an organic non-fossil material of biological origin;
wherein the material of biological origin is one or a mixture of pericarp, leaf, waste oil, wood;
wherein the process is carried out in an inert atmosphere;
wherein the inert atmosphere comprises N 2 And Ar.
10. A catalyst for electrochemical oxygen reduction reactions prepared according to the method of any one of claims 1-9, comprising the structure: has at least 3at% of a hierarchical porous carbon structure with predominantly micropores doped with pyridine nitrogen and pyrrole nitrogen, and the catalyst does not contain a metal.
11. The catalyst of claim 10, wherein the hierarchical porous carbon structure has 50-100% micropores with a size less than 2 nm.
12. The catalyst of claim 11, wherein the hierarchical porous carbon structure has 60-90% of micropores with a size less than 2 nm.
13. The catalyst of claim 12, wherein the hierarchical porous carbon structure has 70-80% micropores with a size less than 2 nm.
14. The catalyst of claim 10, wherein the hierarchical porous carbon structure is 50-100% doped with pyridine nitrogen and pyrrole nitrogen.
15. The catalyst of claim 14, wherein the hierarchical porous carbon structure is 60-90% doped with pyridine nitrogen and pyrrole nitrogen.
16. The catalyst of claim 15, wherein the hierarchical porous carbon structure is 70-80% doped with pyridine nitrogen and pyrrole nitrogen.
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| CN110054168A (en) * | 2019-04-24 | 2019-07-26 | 中国矿业大学 | A kind of preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst |
| CN110038612B (en) * | 2019-05-05 | 2020-09-15 | 中南大学 | N-doped microporous carbon sphere ORR catalytic material and preparation method and application thereof |
| CN110304620A (en) * | 2019-06-25 | 2019-10-08 | 南京师范大学 | It is a kind of to utilize nitrogen-doped porous carbon material made of bean dregs and its preparation method and application |
| CN110492114B (en) * | 2019-08-20 | 2022-06-17 | 大连海事大学 | Nitrogen-doped porous carbon-oxygen reduction catalyst and preparation method and application thereof |
| CN110841595A (en) * | 2019-12-02 | 2020-02-28 | 国网江苏省电力有限公司电力科学研究院 | Preparation method and application of nitrogen-doped graphitized carbon material |
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| CN111495405B (en) * | 2020-03-11 | 2023-03-21 | 江苏大学 | Preparation method of nitrogen-doped carbon foam cathode oxygen reduction catalyst |
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| CN114180553B (en) * | 2021-12-03 | 2023-10-20 | 曲阜师范大学 | Method for preparing nitrogen-doped porous carbon by taking waste crop root system as raw material and application |
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