WO2022142155A1 - 宽pH范围氧还原电催化用氮磷掺杂多孔碳的制备方法 - Google Patents

宽pH范围氧还原电催化用氮磷掺杂多孔碳的制备方法 Download PDF

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WO2022142155A1
WO2022142155A1 PCT/CN2021/099599 CN2021099599W WO2022142155A1 WO 2022142155 A1 WO2022142155 A1 WO 2022142155A1 CN 2021099599 W CN2021099599 W CN 2021099599W WO 2022142155 A1 WO2022142155 A1 WO 2022142155A1
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nitrogen
phosphorus
doped
porous carbon
doped porous
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徐朗
齐佳伟
江海深
白沛瑶
刘伟琪
金柏霖
张文都
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China University of Mining and Technology CUMT
China University of Mining and Technology Beijing CUMTB
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China University of Mining and Technology Beijing CUMTB
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Definitions

  • the invention belongs to the fields of inorganic nanomaterials and electrochemistry, and in particular relates to a preparation method of nitrogen-phosphorus-doped porous carbon for oxygen reduction electrocatalysis in a wide pH range.
  • Fuel cell is a clean energy conversion device that can convert chemical energy into electrical energy with high conversion efficiency and very little pollutant generation. It has long been regarded as one of the effective development approaches to deal with global environmental problems and energy crisis. However, the sluggish kinetics of the cathodic oxygen reduction reaction (ORR) remains a major obstacle for the large-scale application of fuel cells.
  • ORR cathodic oxygen reduction reaction
  • platinum-based catalyst materials and other noble metal-based catalyst materials play a major role in accelerating the rate of cathode catalytic reactions.
  • platinum-based materials and precious metal materials often have many disadvantages, such as high cost, poor durability, and poor resistance to poisoning.
  • heteroatom-doped carbon materials have significant advantages: heteroatom-doped carbon materials not only combine the excellent structural tunability, electrical conductivity, and chemical/thermal stability of porous carbon, but also bring high efficiency through unique heteroatom intercalation. the catalytic site. Simulation calculations and experimental data show that doping heteroatoms into carbon materials can redistribute the electron spin and charge densities of adjacent carbons, while optimizing the chemisorption energy of carbon materials for oxygen molecules and some intermediates, thereby increasing the heterogeneity. ORR catalytic activity of atomically doped carbon materials.
  • the diatomic doping of nitrogen and phosphorus in the same main group can play a more synergistic role to facilitate the ORR reaction, and phosphorus with a larger atomic radius is conducive to the sp 3 orbital configuration, which correspondingly produces a high degree of distortion of the carbon structure and forms Many open edge/defect sites, while the nitrogen doping effect can be tuned.
  • the pore structure and electrical conductivity of carbon materials are also very important. This ensures that carbon materials have highly exposed active sites, fast proton and electron transport, and reciprocal catalytic three-phase boundaries when applied to electrochemical reactions.
  • natural substances derived from nature are a cost-effective, abundant and high-quality carbon source, including minerals and by-products - coal, coal tar, coal tar pitch, petroleum coke, petroleum pitch, etc., as well as agricultural and forestry wastes Wait.
  • supercapacitor electrode materials such as patents CN109637831A, CN111268675A and CN107610945A.
  • the reported studies of oxygen reduction electrocatalysts for fuel cells are far from enough, especially the non-noble metal catalyst materials available over a wide pH range.
  • the invention utilizes the natural mineral-based carbon source represented by coal, and by adjusting the chemical reaction sequence, the nitrogen-phosphorus-doped porous carbon material can be simply and effectively obtained by a two-step pyrolysis method. Benefiting from the abundant nitrogen-phosphorus-related active species and excellent multi-scale pore system, the synthesized metal-free carbon materials exhibit remarkable oxygen reduction electrocatalytic effects in a wide pH range, showing promising development prospects.
  • One of the objectives of the present invention is to provide a preparation method of nitrogen-phosphorus-doped porous carbon material for oxygen reduction electrocatalysis in a wide pH range, which is cost-effective, green, sustainable, and has scalable application value.
  • the technical scheme adopted in the present invention is as follows: a preparation method of natural mineral-based nitrogen and phosphorus doped porous carbon, comprising the following steps:
  • the secondary carbonized product is treated with 1 mol L -1 dilute hydrochloric acid solution at 40-60 °C. Washing for 1-3h, filtering, washing with water until the filtrate is neutral, and drying to obtain a nitrogen-phosphorus-doped porous carbon material.
  • the natural mineral-based carbon source is one or more of coal, coal tar, coal tar, petroleum tar, and petroleum coke.
  • the carbonization temperature is 650°C.
  • the nitrogen dopant is one or more of melamine, dicyandiamide, urea, pyridine, pyrrole, aniline, amino acid and purine
  • the activator is potassium hydroxide, One or more of sodium hydroxide, potassium bicarbonate, sodium bicarbonate, potassium carbonate and sodium carbonate.
  • the mass ratio of carbon to be doped (pretreated natural mineral-based carbon source or primary phosphorus-doped carbon), nitrogen dopant and activator is 1:4:2.
  • the carbonization temperature is 900°C.
  • the carbonization time of the nitrogen doping process is 2h, and the carbonization time of the phosphorus doping process is 1h.
  • the heating rate of the tube furnace is 3°C min ⁇ 1 .
  • the phosphorus dopant is phosphoric acid, triphenylphosphine, phytic acid, red phosphorus, black phosphorus, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dihydrogen phosphate
  • the phosphorus dopant is phosphoric acid, triphenylphosphine, phytic acid, red phosphorus, black phosphorus, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dihydrogen phosphate
  • the phosphorus dopant is phosphoric acid, triphenylphosphine, phytic acid, red phosphorus, black phosphorus, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dihydrogen phosphate
  • sodium, magnesium phosphate, calcium phosphate, diammonium phosphate and diammonium phosphate is sodium, magnesium phosphate, calcium phosphate, diammonium
  • the sample and the phosphorus dopant are mixed by ultrasonic, and the specific ultrasonic parameters are 25Hz (5min), 33Hz (10min), 40Hz (5min), 59Hz (10min), and the total time is 0.5h.
  • the mass ratio of carbon to be doped (primary nitrogen-doped carbon or pretreated natural mineral-based carbon source) to phosphorus dopant is 1:4.
  • the nitrogen and phosphorus contents of the representative nitrogen-phosphorus-doped porous carbon prepared by the nitrogen-first-phosphorus method are respectively 2.5-3.0% and 2.0-2.5%, and the ratio of graphitic nitrogen/pyridine nitrogen is Between 2-3, the ratio of P-C bond to P-O bond is between 2-2.5, which is precisely controllable.
  • the nitrogen and phosphorus contents of the representative nitrogen-phosphorus-doped porous carbon prepared by the phosphorus-first-nitrogen method are around 2.0% and 0.5%, respectively, and the ratio of graphitic nitrogen/pyridine nitrogen is between 1.5 and 2.0, and the proportion of P-C bonds is greater than P-O ratio.
  • the specific surface area of the representative nitrogen-phosphorus-doped porous carbon prepared by the nitrogen-first-phosphorus method is controlled at 820-860 m 2 g -1 , including micropores of 650-670 m 2 g -1 and 170-190 m 2 g - 1 of the middle hole.
  • the specific surface area of the representative nitrogen-phosphorus-doped porous carbon prepared by the phosphorus-first-nitrogen method is controlled at 1200-1240 m 2 g -1 , including micropores of 500-510 m 2 g -1 and 700-730 m 2 g - 1 medium hole, precise and controllable.
  • the present invention has the following beneficial effects:
  • the present invention uses natural mineral-based carbon sources with low cost and abundant earth reserves as raw materials, and can sustainably prepare two nitrogen-phosphorus-doped porous carbon materials by adjusting the chemical reaction sequence.
  • the preparation process is simple and feasible, the cost is low, the intrinsic value of natural substances can be tapped, and the requirements of clean production and sustainable utilization are met.
  • the final nitrogen-phosphorus-doped carbon material is synthesized through the nitrogen-doping step and the phosphorus-doping step, respectively.
  • the nitrogen dopant and the activator can synergize at high temperature to efficiently incorporate an appropriate amount of nitrogen atoms into the carbon framework of natural origin and simultaneously create a rich pore structure;
  • High-temperature etching of phosphorus dopants can create additional defects/edge sites through nitrogen removal and lattice remodeling by replacing some carbon atoms or removing some dopant nitrogen atoms and inserting some phosphorus atoms on the carbon plane
  • doping phosphorus active species optimizing the doping nitrogen type, and expanding the pore structure again.
  • the optimized nitrogen-phosphorus doped carbon material has a large proportion of graphitic nitrogen, phosphorus-carbon bonds and defects as the main active species, a large number of micropores provide a place for catalytic reactions to occur, and suitable mesopores are suitable for the transfer of catalytic related substances.
  • the excellent flake morphology is beneficial for charge transfer.
  • the representative carbon material N 4 P 4 C-900 prepared by doping with nitrogen first and then phosphorus has a relatively regular sheet-like morphology, abundant defect sites and edge layers, and a high specific surface area of 845.5m 2 g –1 , excellent ratio of micropores to mesopores (the specific surface areas of micropores and mesopores are 661.8 and 183.7 m 2 g –1 , respectively), effective doping nitrogen content (2.64%) and doping phosphorus content (2.42%), optimized
  • the unique graphitic nitrogen configuration and phosphorus-carbon bonding site, as well as the remarkable electrolyte wettability can provide sufficient catalytic active sites and electrochemically effective specific surface area and transport channels for related substances for the oxygen reduction electrocatalytic reaction.
  • N 4 P 4 C-900 The two optimized carbon materials obtained by the "nitrogen-phosphorus sequential doping method" showed good electrochemical performance as electrocatalysts for oxygen reduction reaction in a wide pH range, especially N 4 P 4 C-900.
  • the initial potential of N 4 P 4 C-900 is 0.97V
  • the half-wave potential is 0.85V
  • the limiting current density is 6.36mA cm -2
  • the initial potential of N 4 P 4 C-900 is 0.82V
  • the half-wave potential is 0.65V
  • the limiting current density is 6.48mA cm -2
  • N 4 The onset potential of P 4 C-900 was 0.87 V
  • the half-wave potential was 0.67 V
  • the limiting current density was 7.12 mA cm -2 .
  • N 4 P 4 C-900 has lower hydrogen peroxide production and a nearly four-electron catalytic reaction pathway
  • N 4 P 4 C-900 has better cycle stability and anti-impurity poisoning performance than commercial platinum carbon catalysts.
  • N 4 P 4 C-900 has excellent power density and discharge performance in Zn-air batteries.
  • Example 1 is a low-magnification scanning electron microscope (SEM) image of the nitrogen-phosphorus-doped porous carbon N 4 P 4 C-900 prepared in Example 2 of the present invention.
  • Example 2 is a high-magnification scanning electron microscope (SEM) image of the nitrogen-phosphorus-doped porous carbon N 4 P 4 C-900 prepared in Example 2 of the present invention.
  • Example 3 is a high-resolution transmission electron microscope (HRTEM) image of the nitrogen-phosphorus-doped porous carbon N 4 P 4 C-900 prepared in Example 2 of the present invention.
  • HRTEM transmission electron microscope
  • Example 4 is an X-ray diffraction (XRD) pattern of the nitrogen-phosphorus-doped porous carbon N 4 P 4 C-900 prepared in Example 2 of the present invention.
  • XRD X-ray diffraction
  • FIG. 5 is a Raman spectrum diagram of nitrogen-phosphorus doped porous carbons P 4 N 4 C-900 and N 4 P 4 C-900 prepared in Examples 1 and 2 of the present invention.
  • FIG. 6 is a nitrogen peak diagram of X-ray photoelectron spectroscopy (XPS) of nitrogen-phosphorus doped porous carbons P 4 N 4 C-900 and N 4 P 4 C-900 prepared in Examples 1 and 2 of the present invention.
  • XPS X-ray photoelectron spectroscopy
  • Fig. 7 shows the detailed data of XPS surface composition of typical carbon materials obtained.
  • FIG. 8 is a phosphorus peak diagram of X-ray photoelectron spectroscopy (XPS) of nitrogen-phosphorus doped porous carbons P 4 N 4 C-900 and N 4 P 4 C-900 prepared in Examples 1 and 2 of the present invention.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 10 is the obtained detailed data on the specific surface area and pores of a typical carbon material.
  • FIG 11 is a graph showing the pore size distribution curves of the nitrogen-phosphorus doped porous carbons P 4 N 4 C-900 and N 4 P 4 C-900 prepared in Examples 1 and 2 based on a density functional theory (DFT) model.
  • DFT density functional theory
  • Example 12 is a cyclic voltammetry (CV) diagram of the nitrogen-phosphorus-doped porous carbon N 4 P 4 C-900 prepared in Example 2 of the present invention in a 0.1 mol L -1 KOH solution.
  • CV cyclic voltammetry
  • Fig. 13 is the linear sweep voltammetry (LSV) curve of the nitrogen-phosphorus doped porous carbon N 4 P 4 C-900 prepared in Example 2 of the present invention in 0.1 mol L -1 KOH solution at 10 mV s -1 at each rotational speed .
  • LSV linear sweep voltammetry
  • Figure 14 shows the nitrogen-phosphorus doped porous carbons P 4 N 4 C-900 and N 4 P 4 C-900 and 20% Pt/C in 0.1 mol L -1 KOH solution 10mV prepared in Examples 1 and 2 of the present invention Comparison chart of LSV at 1600rpm at s -1 .
  • Figure 15 shows the nitrogen-phosphorus doped porous carbons N 4 P 4 C-900 and N 4 P 4 C-900-d prepared in Examples 2 and 3 of the present invention in 0.1 mol L -1 KOH solution at 10mV s -1 1600rpm LSV comparison chart.
  • Figure 16 is the rotating ring-disk electrode test (RRDE) of nitrogen-phosphorus doped porous carbon N 4 P 4 C-900 and 20% Pt/C in 0.1 mol L -1 KOH solution prepared in Example 2 of the present invention Hydrogen peroxide yield and electron transfer number map.
  • RRDE rotating ring-disk electrode test
  • Figure 17 shows the cycle of the nitrogen-phosphorus doped porous carbon N 4 P 4 C-900 and 20% Pt/C in 0.1 mol L -1 KOH solution at 0.82 V vs. RHE at 400 rpm speed prepared in Example 2 of the present invention Stability graph.
  • Fig. 18 is the chronocurrent of nitrogen-phosphorus doped porous carbon N 4 P 4 C-900 and 20% Pt/C prepared in Example 2 of the present invention before and after adding 1 mol L -1 methanol to 0.1 mol L -1 KOH solution Compare graphs.
  • Fig. 19 is a comparison diagram of LSV at 1600 rpm before and after adding NO 2 - and SO 3 2- to 0.1 mol L -1 KOH solution of nitrogen-phosphorus doped porous carbon N 4 P 4 C-900 prepared in Example 2 of the present invention .
  • Fig. 20 is the polarization curve and power density graph of the nitrogen-phosphorus doped porous carbon N 4 P 4 C-900 prepared in Example 2 of the present invention measured in a zinc-air battery with a 6.0 mol L -1 KOH solution as the electrolyte .
  • Figure 21 shows the difference measured in the zinc-air battery using nitrogen-phosphorus doped porous carbon N 4 P 4 C-900 prepared in Example 2 and 20% Pt/C in 6.0 mol L -1 KOH solution as electrolyte Plot of galvanostatic discharge curves at current density.
  • Figure 22 shows the nitrogen-phosphorus doped porous carbons P 4 N 4 C-900 and N 4 P 4 C-900 and 20% Pt/C in 0.5mol L -1 H 2 SO 4 prepared in Examples 1 and 2 of the present invention Comparison of LSV at 1600rpm at 10mV s -1 in solution.
  • FIG. 24 is an LSV diagram of nitrogen-phosphorus-doped carbon 1 prepared in Comparative Example 1 of the present invention in 0.1 mol L -1 KOH at 10 mV s -1 at 1600 rpm.
  • Figure 25 is the LSV diagram of the nitrogen-phosphorus-doped carbon 2 prepared in Comparative Example 2 of the present invention in 0.5 mol L -1 H 2 SO 4 at 10 mV s -1 at 1600 rpm.
  • FIG. 26 is the LSV diagram of the nitrogen-phosphorus-doped carbon 2 prepared in Comparative Example 2 of the present invention in 0.1 mol L ⁇ 1 PBS at 10 mV s ⁇ 1 at 1600 rpm.
  • the pretreated coal, melamine and potassium hydroxide were weighed in a mass ratio of 1:4:2, ground and mixed, and then transferred to a tube furnace, carbonized at 850 °C for 2 h under a nitrogen atmosphere, taken out after carbonization, and processed by Pickling, filtration, water washing, and drying to obtain nitrogen-doped carbon; respectively weighing nitrogen-doped carbon and phosphoric acid in a mass ratio of 1:4, adding water, diluting, ultrasonically mixing, drying, and transferring to a tube furnace, and in a nitrogen atmosphere at Carbonized at 850°C for 1 h to obtain secondary carbonized product; the secondary carbonized product was acid-washed with 1 mol L -1 dilute hydrochloric acid solution at 40-60 °C for 1-3 h, filtered, washed with water until the filtrate was neutral, and dried to obtain nitrogen Phosphorus-doped porous carbon material N 4 P 4 C-850.
  • the pretreated coal, melamine and potassium hydroxide were weighed in a mass ratio of 1:4:2, ground and mixed, and then transferred to a tube furnace, carbonized at 950 °C for 2 h under a nitrogen atmosphere, taken out after carbonization, and processed by Pickling, filtration, water washing, and drying to obtain nitrogen-doped carbon; respectively weighing nitrogen-doped carbon and phosphoric acid in a mass ratio of 1:4, adding water, diluting, ultrasonically mixing, drying, and transferring to a tube furnace, and in a nitrogen atmosphere at Carbonized at 950°C for 1 h to obtain secondary carbonized product; the secondary carbonized product was acid-washed with 1 mol L -1 dilute hydrochloric acid solution at 40-60 °C for 1-3 h, filtered, washed with water until the filtrate was neutral, and dried to obtain nitrogen Phosphorus-doped porous carbon material N 4 P 4 C-950.
  • Phosphoric acid diluted with water, ultrasonically mixed, dried and transferred to a tube furnace, carbonized at 900 °C for 1 h in a nitrogen atmosphere to obtain a secondary carbonized product; the secondary carbonized product was diluted with 1 mol L -1 at 40-60 °C Pickled with hydrochloric acid solution for 1-3 hours, filtered, washed with water until the filtrate is neutral, and dried to obtain a series of nitrogen-phosphorus doped porous carbon materials.
  • Use ground biomass as raw material carbonize at 500 °C for 1 hour, and obtain pre-carbonized material after cooling; mix potassium hydroxide, potassium bicarbonate and pre-carbonized material in a mass ratio of 2:1:1, and press 5% nitrogen
  • the amount of element doping was doped with melamine, mixed with deionized water, soaked in a water bath at 80 °C and dried to obtain nitrogen-doped carbon; activated at 800 °C for 2.67 h in a nitrogen atmosphere, and then taken out and ground; then 5% phosphorous acid was added.
  • 2g potassium phytate was calcined at 800°C for 1h under nitrogen atmosphere, the heating rate was 3°Cmin -1 , after natural cooling, it was treated with hydrochloric acid at room temperature for 18h and washed with deionized water until the precipitate was neutrally dried to obtain phosphorus-doped carbon; then take 0.1 G phosphorus-doped carbon was ground and mixed with 2 g of melamine, heat-treated at a high temperature of 1000 °C for 2 h, washed with water, centrifuged and dried to obtain nitrogen-phosphorus-doped carbon 3.
  • the representative nitrogen-phosphorus-doped porous carbon material N 4 P 4 C-900 prepared in Example 2 exhibited a large amount of dispersed rough carbon under a low-resolution scanning electron microscope (SEM), as shown in Fig.
  • SEM scanning electron microscope
  • FIG. 2 Provide abundant specific surface area and pore structure, further high-resolution SEM display, as shown in Figure 2, it can be seen that the sheet layer of the carbon material is very thin, with different layered edges, and there are certain differences between different carbons. With a degree of cross-linking, this structure facilitates electron transfer and related species transport.
  • TEM Transmission electron microscopy
  • the nitrogen doping process of melamine and potassium hydroxide in the first step and the phosphoric acid etching process in the second step will create certain pores, and the phosphoric acid in the second step can etch the carbon at high temperature to make it thinner and the edge More points, which facilitates the accessibility of electrolyte and oxygen for the subsequent catalytic process.
  • the etching of phosphoric acid in the second step will remove some nitrogen atoms and cause the lattice remodeling of carbon and the introduction of doped phosphorus atoms, thus bringing corresponding internal vacancy defects, topological defects and edge defects, forming more catalytic active sites point.
  • Figure 4 is the XRD test pattern of N 4 P 4 C-900 material.
  • the material has two characteristic peaks around 24.1° and 41.6°, which are attributed to the (002) and (101) planes of graphitic carbon, respectively.
  • N 4 P 4 C-900 has a large degree of disorder, which indirectly proves that the material has a large number of pores. This is beneficial to the infiltration of electrolyte ions and the transport of related species.
  • Examples 1 and 2 were tested for material surface elements and content using an X-ray photoelectron spectroscopy (XPS) analyzer.
  • XPS X-ray photoelectron spectroscopy
  • Both P4N4C - 900 and N4P4C - 900 have higher carbon content and some oxygen, nitrogen, phosphorus content.
  • Figure 6 shows the high-resolution nitrogen peaks of P 4 N 4 C-900 and N 4 P 4 C-900, P 4 N 4 C-900 and N 4 P 4 C-900 contain 2.0% and 2.64% nitrogen, respectively Atoms, the ratios of pyridine nitrogen (N-6), pyrrolic nitrogen (N-5), graphitic nitrogen (NQ) and nitrogen oxide (NO) of P 4 N 4 C-900 are 21.6% and 18.6%, respectively, by peak calculation.
  • FIG. 7 shows the proportions of pyridine nitrogen, pyrrolic nitrogen, graphitic nitrogen and nitrogen oxide of N 4 P 4 C-900.
  • Figure 8 shows the high-resolution phosphorus peaks of P 4 N 4 C-900 and N 4 P 4 C-900. According to the peak calculation, P 4 N 4 C-900 has a phosphorus content of 0.49%, including 55.6% of PC. bonds and 44.4% PO bonds; while N 4 P 4 C-900 has a phosphorus content of 2.42%, including 70.2% PC bonds and 29.8% PO bonds.
  • N 4 P 4 C-900 has more nitrogen content and phosphorus content than P 4 N 4 C-900, and the ratio of graphitic nitrogen and phosphorus carbon bonds of N 4 P 4 C-900 is more prominent.
  • the nitrogen and phosphorus contents of P 4 N 4 C-900 prepared by the method of Example 1 are 2.0% and 0.5%, respectively, and the ratio of graphitic nitrogen/pyridine nitrogen is 1.71, and the ratio of PC bond to PO bond is 1.25; Compared with P4C - 900, some nitrogen content was increased and much phosphorus content was decreased.
  • N 4 P 4 C-900 The nitrogen and phosphorus contents of N 4 P 4 C-900 prepared by the method of Example 2 are 2.64% and 2.42%, respectively, and the ratio of graphitic nitrogen/pyridine nitrogen is 2.72, and the ratio of PC bond to PO bond is 2.35; Compared with N 4 C-900, some nitrogen content is reduced and a lot of phosphorus content is supplemented, and the content and type of heteroatom doping are precisely controllable.
  • Graphitic nitrogen and PC bonds can change the charge density and spin density of adjacent carbons, and act as active species in oxygen reduction electrocatalysis. wetness. In addition, graphitic nitrogen species also contribute to the electrical conductivity of carbon materials.
  • FIG. 9 is a graph of nitrogen adsorption/desorption of P4N4C - 900 and N4P4C - 900, both of which are typical microporous materials, and the curves are nearly vertical in the low pressure range near 0 The trend also confirms the presence of a large number of micropores in the material.
  • the specific surface areas of P 4 N 4 C-900 and N 4 P 4 C-900 are 1220.7 and 845.5 m 2 g ⁇ 1 , respectively; the pore volumes are 1.135 and 0.594 cm 3 g ⁇ 1 , respectively.
  • P 4 N 4 C-900 has micropores of 503.2m 2 g –1 and mesopores of 717.5m 2 g –1 , which is further improved compared with the specific surface area of P 4 C-900, which is 866.2m 2 g –1 . The surface area is reduced and the mesopore specific surface area is greatly increased.
  • N 4 P 4 C-900 has micropores of 661.8m 2 g –1 and mesopores of 183.7m 2 g –1 , which is significantly higher than the specific surface area of N 4 C-900 of 629.8m 2 g –1 . and mesopore specific surface area both increased and the mesopore specific surface area was about doubled, as shown in Fig.
  • P 4 N 4 C-900 and N 4 P 4 C-900 have good controllability of variation .
  • the pore size distribution curves of P 4 N 4 C-900 and N 4 P 4 C-900 are obtained through DFT model analysis.
  • Figure 11 The pore size distribution of P 4 N 4 C-900 samples is concentrated at 0.50, 0.85 and 3.14 nm, respectively.
  • N 4 The pore size distribution of P 4 C-900 samples are concentrated at 0.52, 0.83 and 2.71 nm, respectively. It can be seen that both P 4 N 4 C-900 and N 4 P 4 C-900 have micropores with larger pore size and a certain proportion of mesopores.
  • micropores can provide actual reaction sites for the catalytic reaction, and the mesopores can facilitate the Mass transfer and transfer of related substances, the synergistic effect of micropores and mesopores enables more active sites to play a role, ensuring excellent catalytic efficiency.
  • the preparation process of the working electrode is as follows: Weigh 3-5 mg of the prepared nitrogen-phosphorus doped porous carbon material into a centrifuge tube, then add 80-160 ⁇ L of isopropanol, 160-320 ⁇ L of water and 10-20 ⁇ L of perfluorosulfonic acid-polyethylene The tetrafluoroethylene copolymer was prepared into 250-500 ⁇ L suspension and ultrasonicated for 30 minutes to form a well-dispersed black mucus, and then 5-15 ⁇ L of the mucus was dropped on the glassy carbon electrode to dry to prepare a working electrode. The Ag/AgCl electrode was used as a reference. The oxygen reduction electrocatalytic performance was tested on the workstation with platinum wire as the counter electrode.
  • Example 2 The samples N 4 P 4 C-900 and 20% Pt/C of Example 2 were subjected to CV, LSV and RRDE tests in a 0.1 mol L -1 KOH solution in a constant temperature water bath at 25 °C. Small molecule testing and alkaline zinc-air battery testing. As shown in Figure 12-21.
  • N 4 P 4 C-900 exhibits an approximately rectangular electrochemical feature in N 2 , which is attributed to the capacitive properties of the material; it has a better redox peak in O 2 , and the peak potential is 0.872V vs. RHE, showing good catalytic potential of the prepared electrode material.
  • Fig. 13 the LSV curves of N 4 P 4 C-900 at different rotational speeds, with the increase of rotational speed, the current density increases uniformly. In the high-potential region, the material exhibits a better catalytic potential, which is derived from the kinetic control; in the low-potential region, the material exhibits a better current density, which is derived from the oxygen diffusion control.
  • N 4 P 4 C-900 exhibits an onset potential and half-wave potential better than 20% Pt/C, which is also better than P 4 N 4 C-900.
  • the onset potential of N 4 P 4 C-900 is 0.97 V
  • the half-wave potential is 0.85 V
  • the limiting current density is 6.36 mA cm ⁇ 2 at standard RHE potential.
  • Figure 15 shows that N4P4C-900 prepared by the variable frequency ultrasonic mixing method has significantly better performance than N4P4C - 900 - d prepared by direct mixing, highlighting the variable frequency ultrasonication developed in this patent The importance of the hybrid method for the properties and electrochemical performance of the prepared materials!
  • the RRDE test and calculation show that at 0.3-0.9V vs. RHE potential, the N 4 P 4 C-900 hydrogen peroxide yield is lower than 2.13%, and the electron transfer number is higher than 3.96, which is similar to Pt /C performed similarly, confirming that the N 4 P 4 C-900 oxygen reduction electrocatalytic process undergoes a dominant four-electron pathway.
  • the excellent catalytic performance of N 4 P 4 C-900 under alkaline conditions benefits from the abundant nitrogen and phosphorus related active sites brought about by the two-step pyrolysis method of nitrogen doping and phosphorus etching, as well as for the transfer of nitrogen and phosphorus.
  • a qualitatively interconnected micropore-mesoporous structure As can be seen from Figure 16, the RRDE test and calculation show that at 0.3-0.9V vs. RHE potential, the N 4 P 4 C-900 hydrogen peroxide yield is lower than 2.13%, and the electron transfer number is higher than 3.96, which is similar to Pt /C performed
  • the N 4 P 4 C-900 in Example 2 was tested by it chronoamperometry at 400rpm in 0.1mol L -1 KOH electrolyte, while 20% Pt/C was tested under the same conditions for comparison, as shown in the figure 17 shown.
  • the current retention of N 4 P 4 C-900 after 30000 s cycling was 95.45%, which was much higher than the stability of 20% Pt/C of 68.40%.
  • the N 4 P 4 C-900 and 20% Pt/C in Example 2 were tested for methanol resistance in 0.1 mol L -1 KOH electrolyte, as shown in FIG. 18 .
  • N 4 P 4 C-900 Through it chronoamperometry test, adding methanol at 200s, the catalytic activity of N 4 P 4 C-900 remained basically unchanged, while the Pt/C catalyst had obvious methanol oxidation reaction.
  • the N 4 P 4 C-900 in Example 2 was tested against small organic molecules (NaNO 2 and NaHSO 3 ) in 0.1 mol L -1 KOH electrolyte, as shown in Figure 19, and NaNO 2 and NaHSO were added to the electrolyte, respectively After 3 , N 4 P 4 C-900 maintained relatively stable catalytic performance, and the catalytic performance could be completely recovered after being replaced with fresh electrolyte.
  • N 4 P 4 C-900 shows great application potential in alkaline fuel cells and metal-air batteries.
  • N4P4C - 900 exhibited better half-wave potential and limiting current density than 20% Pt/C, and this was significantly better than P4N4C - 900.
  • the onset potential of N 4 P 4 C-900 was 0.82 V
  • the half-wave potential was 0.65 V
  • the limiting current density was 6.48 mA cm ⁇ 2 at standard RHE potential.
  • N 4 P 4 C-900 material still has excellent catalytic effect under acidic conditions.
  • the excellent catalytic performance of N 4 P 4 C-900 under acidic conditions benefits from the high proportion of graphitic nitrogen and phosphorus carbon bond species and abundant defects obtained by the two-step sequential doping method.
  • N 4 P 4 C-900 showed better half-wave potential and limiting current density than 20% Pt/C, which was also significantly better than P 4 N 4 C-900.
  • the onset potential of N 4 P 4 C-900 was 0.87 V
  • the half-wave potential was 0.67 V
  • the limiting current density was 7.12 mA cm ⁇ 2 at standard RHE potential. This shows that the material has great potential for application to biofuel cells.
  • the excellent catalytic performance of N 4 P 4 C-900 under neutral conditions benefits from the nitrogen and phosphorus doping sites obtained by the two-step sequential doping method and the abundant defect and pore structure suitable for neutral ions.
  • nitrogen-phosphorus doped carbon 1 is obtained, as described in patent CN107610945A, which can be used as a supercapacitor electrode material.
  • the electrocatalytic performance of the representative nitrogen-phosphorus doped carbon 1 in the alkaline 0.1M KOH electrolyte is relatively poor, and it does not have the potential to be used as a fuel cell cathode catalyst.
  • This also highlights the importance of the methods of Examples 1 and 2 of the present invention for obtaining oxygen reduction catalysts usable over a wide pH range.
  • nitrogen-phosphorus doped carbon 3 obtained according to Comparative Example 3 can have a certain electrocatalytic activity in an alkaline 0.1M KOH electrolyte.
  • this patent does not mention the ORR electrocatalytic performance of the material under acidic and neutral conditions, indicating that the representative nitrogen-phosphorus doped carbon 3 has insufficient electrocatalytic performance in acidic and neutral electrolytes, and does not have the same electrocatalytic performance under acidic and neutral conditions. potential as a cathode catalyst.
  • This also highlights the importance of the methods of Examples 1 and 2 of the present invention for obtaining oxygen reduction catalysts usable over a wide pH range.

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Abstract

提供了一种宽pH范围氧还原电催化用氮磷掺杂多孔碳的制备方法，以天然矿物基碳源为原料，利用"氮磷顺序掺杂法"分两条路径进行合成。成本效益高，制备方法可持续、可规模化；变频超声混合方法保证了较高性能。制备的氮磷掺杂多孔碳具有分散的片状形貌，丰富的边缘和缺陷，大的比表面积和孔容，充足的微孔和中孔以及适量的掺杂氮和掺杂磷，作为氧还原反应电催化剂在碱性电解液、酸性电解液与中性电解液中均显示出良好的电化学催化性能，并具有良好的抗小分子和甲醇毒化的能力，在碱性燃料电池/金属空气电池、质子交换膜燃料电池(酸性电解质)和生物燃料电池(中性电解质)中具有很好的应用潜力。

Description

宽pH范围氧还原电催化用氮磷掺杂多孔碳的制备方法 技术领域
本发明属于无机纳米材料及电化学领域，具体涉及宽pH范围氧还原电催化用氮磷掺杂多孔碳的制备方法。
背景技术
燃料电池是一种可以将化学能转化为电能、转换效率高、污染物产生量极少的清洁能源转换装置，长期以来被认为是应对全球环境问题和能源危机的有效发展途径之一。然而，阴极氧还原反应(ORR)缓慢的动力学仍然是燃料电池大规模应用的主要障碍。目前，铂基催化剂材料和其他贵金属基催化剂材料在加速阴极催化反应速率方面发挥着较大的作用。但是，铂基材料与贵金属材料往往存在成本高、耐久性差、抗毒化能力差等诸多缺点。另外，大多数的研究集中在碱性介质中电催化材料的发展，酸性燃料电池如质子交换膜燃料电池的商业化发展也是至关重要的，但却存在着更大的挑战，这是因为在酸性介质中所研究的电催化材料普遍存在性能低、性能易衰减以及很多副反应发生的情况。与此同时，生物燃料电池作为另一种很有前途的可再生能源设备需要依赖于内部的中性环境。因此，以碱性燃料电池、质子交换膜燃料电池(酸性电解质)和生物燃料电池(中性电解质)为研究对象，开发高活性、原料来源丰富、长期稳定、不受介质影响的在宽pH值范围内通用的贵金属替代电催化剂是非常必要的。
其中，杂原子掺杂碳材料具有显著优势：杂原子掺杂碳材料不仅结合了多孔碳的优异结构可调性、导电性和化学/热稳定性，而且通过独特的杂原子嵌入带来了高效的催化位点。模拟计算和实验数据表明，将杂原子掺杂到碳材料中可以重新分配相邻碳的电子自旋密度和电荷密度，同时优化碳材料对氧气分子和一些中间体的化学吸附能，从而提高杂原子掺杂碳材料的ORR催化活性。其中，处于同一主族的氮与磷双原子掺杂更能起到协同作用以利于ORR反应,具有较大原子半径的磷有利于sp 3轨道构型，相应地产生碳结构的高度畸变并形成许多开放的边缘/缺陷位点，同时可以调节氮的掺杂效果。
此外，碳材料的孔隙结构和电导性同样非常重要。这能够保证碳材料在应用于电化学反应时具有高暴露的活性位点、快速的质子和电子输送以及可交互的催化三相边界。另外，来源于自然界的天然物质是一种具有高成本效益、储量丰富和高品质的碳源，包括矿物及附属产品-煤炭、煤焦油、煤焦油沥青、石油焦、石油沥青等以及农林废弃物等。目前，以超级电容器电极材料为代表的天然物质基能源材料已经有了一定的研究，如专利CN109637831A，CN111268675A和CN107610945A。但已报道的燃料电池氧还原电催化剂的研究还远远不够，尤其是在宽pH值内可用的非贵金属催化剂材料。
鉴于氧还原电催化剂的研究具有很大的研究价值与应用潜力，因此，开发简单、可持续、可大规模生产的制备方法以合成天然物质来源的高效电催化剂具有可贵的现实意义，这不仅挖掘了天然材料的潜在价值，而且符合清洁利用的环保要求。本发明利用以煤炭为代表的天然矿物基碳源，通过调控化学反应次序，只需两步热解法便可简单而有效的获得氮磷掺杂多孔碳材料。得益于丰富的氮磷相关的活性物种和优异的多尺度孔隙系统，合成的无金属碳材料在宽pH范围内均具有显著的氧还原电催化效果，具有较好的发展前景。
发明内容
本发明的目的之一是提供宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，成本效益高，方法绿色、 可持续，具有可规模化的应用价值。
为实现上述目的，本发明采用的技术方案如下：一种天然矿物基氮磷掺杂多孔碳的制备方法，包括以下步骤：
(1)将天然矿物基碳源清洗晾干，然后400-600rpm下混合球磨；保护气体下预碳化；将炭化料在80-90℃条件下用2-3mol L –1氢氧化钾溶液碱洗1-3h，过滤，水洗至滤液呈中性；再在50-60℃条件下用4-6mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，产物烘干，获得预处理后的待掺杂碳源；
(2)按质量比1：2-6：1-3分别称取前一步的待掺杂碳、氮掺杂剂与活化剂，研磨混匀后转移至管式炉中，在氮气气氛下于850-1050℃碳化1-4h，升温速率为2-20℃min –1，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；
(3)按质量比1：3-5分别称取前一步的待掺杂碳与磷掺杂剂，加水稀释混合，之后烘干转移至管式炉中，在氮气气氛下于850-1050℃碳化1-4h，升温速率为2-20℃min –1，经酸洗、过滤、水洗、烘干得到磷掺杂碳；
(4)所述的方法按照(1)(2)(3)或者(1)(3)(2)的步骤将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料。
优选的，步骤(1)中，天然矿物基碳源为煤炭、煤沥青、煤焦油，石油沥青、石油焦的一种或几种。
优选的，步骤(1)中，所述碳化的温度为650℃。
优选的，步骤(2)中，所述氮掺杂剂为三聚氰胺、双氰胺、尿素、吡啶、吡咯、苯胺、氨基酸和嘌呤中的一种或多种，所述活化剂为氢氧化钾、氢氧化钠、碳酸氢钾、碳酸氢钠、碳酸钾和碳酸钠的一种或多种。
优选的，步骤(2)中，待掺杂碳(预处理后的天然矿物基碳源或一次磷掺杂碳)、氮掺杂剂与活化剂的质量比为1：4：2。
优选的，步骤(2)、(3)中，所述碳化的温度为900℃。
优选的，步骤(2)、(3)中，所述氮掺杂过程的碳化时间为2h，所述磷掺杂过程的碳化时间为1h。
优选的，步骤(2)、(3)中，管式炉的升温速率为3℃min –1。
优选的，步骤(3)中，所述磷掺杂剂为磷酸、三苯基膦、植酸、红磷、黑磷、磷酸氢二钾、磷酸二氢钾、磷酸氢二钠、磷酸二氢钠、磷酸镁、磷酸钙、磷酸二氢氨与磷酸氢二氨中的一种或多种。
优选的，步骤(3)中，样品与磷掺杂剂采用超声混合，具体的超声参数为25Hz(5min),33Hz(10min),40Hz(5min),59Hz(10min),总时间0.5h。
优选的，步骤(3)中，待掺杂碳(一次氮掺杂碳或预处理后的天然矿物基碳源)与磷掺杂剂的质量比1：4。
优选的，步骤(4)中，通过先氮后磷法制得的代表性氮磷掺杂多孔碳的氮和磷含量分别在2.5-3.0％和2.0-2.5％，并且石墨氮/吡啶氮的比值在2-3之间，P-C键与P-O键的比值在2-2.5之间，精确可控。通过先磷后氮法制得的代表性氮磷掺杂多孔碳的氮和磷含量分别在2.0％和0.5％附近，并且石墨氮/吡啶氮的比值在1.5-2.0之间，P-C键占比大于P-O占比。
优选的，通过先氮后磷法制得的代表性氮磷掺杂多孔碳的比表面积控制在820-860m 2g –1，包括650-670m 2g –1的微孔和170-190m 2g –1的中孔。优选的，通过先磷后氮法制得的代表性氮磷掺杂多孔碳的比表面积控制在 1200-1240m 2g –1，包括500-510m 2g –1的微孔和700-730m 2g –1的中孔，精确可控。
与现有技术相比，本发明具有如下有益效果：
1、本发明以低成本、地球储量丰富的天然矿物基碳源为原料，通过调控化学反应次序，可持续地制备得到两种氮磷掺杂多孔碳材料。制备工艺简单可行，成本低，可以挖掘天然物质的内在价值，符合清洁生产和可持续利用的要求。
2、本发明分别通过氮掺杂步骤和磷掺杂步骤合成最终的氮磷掺杂碳材料。在氮掺杂步骤中氮掺杂剂和活化剂能够在高温条件下协同作用，在天然来源的碳骨架中高效掺入适量的氮原子并同步创造了丰富的孔隙结构；在磷掺杂步骤中磷掺杂剂的高温刻蚀能够通过替代部分碳原子或脱除一些掺杂氮原子进而在碳平面上嵌入一些磷原子，通过氮原子脱除和晶格重塑来创造额外的缺陷/边缘位点，同步提供掺杂磷活性物种、优化掺杂氮类型以及再次扩充孔隙结构。因此优化的氮磷掺杂碳材料具有大比例的石墨氮、磷碳键、缺陷作为主要的活性物种，大量的微孔为催化反应提供可发生的场所，合适的中孔为催化相关物质的转移提供保障，优异的片状形貌有利于电荷转移。
3、通过先氮后磷掺杂制备的代表性碳材料N 4P 4C-900具有较规则的片状形貌，丰富的缺陷位点和边缘层次，高的比表面积845.5m 2g –1，优异的微孔与中孔比例(微孔与中孔比表面积分别为661.8和183.7m 2g –1)，有效的掺杂氮含量(2.64％)与掺杂磷含量(2.42％)，优化的石墨氮构型和磷与碳连接键位，以及显著的电解液浸润性，这能够为氧还原电催化反应提供充足的催化活性位点和电化学有效比表面积以及相关物质的传输通道。
4、通过“氮磷顺序掺杂法”获得的两种优化碳材料作为氧还原反应电催化剂在宽pH范围内均显示出良好的电化学性能，尤其是N 4P 4C-900。在标准氢电势下，在碱性氢氧化钾电解液条件下，N 4P 4C-900起始电位为0.97V，半波电位为0.85V，极限电流密度为6.36mA cm –2；在酸性硫酸电解液条件下，N 4P 4C-900起始电位为0.82V，半波电位为0.65V，极限电流密度为6.48mA cm –2；在中性磷酸盐缓冲电解液条件下，N 4P 4C-900起始电位为0.87V，半波电位为0.67V，极限电流密度为7.12mA cm –2。此外，N 4P 4C-900具有较低的过氧化氢产出以及接近四电子的催化反应路径。这些催化性能可与相应条件下的商业铂碳催化剂相媲美。
5、得益于合理的孔隙结构和优化的石墨氮与磷碳物种，N 4P 4C-900具有优于商业铂碳催化剂的良好的循环稳定性及抗杂质毒化性能。此外，N 4P 4C-900在锌空气电池中具有优异的功率密度与放电性能。
附图说明
图1为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900的低倍扫描电子显微镜(SEM)图。
图2为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900的高倍扫描电子显微镜(SEM)图。
图3为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900的高分辨透射电子显微镜(HRTEM)图。
图4为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900的X射线衍射(XRD)图。
图5为本发明实施例1和2制得的氮磷掺杂多孔碳P 4N 4C-900和N 4P 4C-900的拉曼(Raman)光谱图。
图6为本发明实施例1和2制得的氮磷掺杂多孔碳P 4N 4C-900和N 4P 4C-900的X射线光电子能谱(XPS)的氮分峰图。
图7为获得的典型碳材料的XPS表面组分详细数据。
图8为本发明实施例1和2制得的氮磷掺杂多孔碳P 4N 4C-900和N 4P 4C-900的X射线光电子能谱(XPS)的磷分峰图。
图9为本发明实施例1和2制得的氮磷掺杂多孔碳P 4N 4C-900和N 4P 4C-900的氮气吸/脱附曲线图。
图10为获得的典型碳材料的比表面积与孔相关的详细数据。
图11为发明实施例1和2制得的氮磷掺杂多孔碳P 4N 4C-900和N 4P 4C-900基于密度泛函理论(DFT)模型的孔径分布曲线图。
图12为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900在0.1mol L –1KOH溶液中的循环伏安曲线(CV)图。
图13为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900在0.1mol L –1KOH溶液中10mV s –1下各个转速的线性扫描伏安曲线(LSV)图。
图14为本发明实施例1和2制得的氮磷掺杂多孔碳P 4N 4C-900和N 4P 4C-900以及20％Pt/C在0.1mol L –1KOH溶液中10mV s –1下1600rpm的LSV对比图。
图15为本发明实施例2和3制得的氮磷掺杂多孔碳N 4P 4C-900和N 4P 4C-900-d在0.1mol L –1KOH溶液中10mV s –1下1600rpm的LSV对比图。
图16为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900与20％Pt/C在0.1mol L –1KOH溶液中的旋转环-圆盘电极测试(RRDE)的过氧化氢产率和电子转移数图。
图17为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900以及20％Pt/C在0.1mol L –1KOH溶液中在0.82V vs.RHE时400rpm转速的循环稳定性图。
图18为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900以及20％Pt/C在0.1mol L –1KOH溶液中加入1mol L –1的甲醇前后的计时电流比较图。
图19为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900在0.1mol L –1KOH溶液中加入NO 2 –和SO 3 2–前后的1600rpm转速的LSV比较图。
图20为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900在6.0mol L –1KOH溶液作为电解液的锌空气电池中测出的极化曲线和功率密度图。
图21为本发明实施例2制得的氮磷掺杂多孔碳N 4P 4C-900以及20％Pt/C在6.0mol L –1KOH溶液作为电解液的锌空气电池中测出的不同电流密度下的恒电流放电曲线图。
图22为本发明实施例1和2制得的氮磷掺杂多孔碳P 4N 4C-900和N 4P 4C-900以及20％Pt/C在0.5mol L –1H 2SO 4溶液中10mV s –1下1600rpm的LSV对比图。
图23为本发明实施例1和2制得的氮磷掺杂多孔碳P 4N 4C-900和N 4P 4C-900以及20％Pt/C在磷酸盐缓冲溶液(0.1M PBS，pH＝7.0)中10mV s –1下1600rpm的LSV对比图。
图24为本发明对比实施例1制得的氮磷掺杂炭1在0.1mol L –1KOH中10mV s –1下1600rpm的LSV图。
图25为本发明对比实施例2制得的氮磷掺杂炭2在0.5mol L –1H 2SO 4中10mV s –1下1600rpm的LSV图。
图26为本发明对比实施例2制得的氮磷掺杂炭2在0.1mol L –1PBS中10mV s –1下1600rpm的LSV图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
以下实施例中所用的天然矿物基原料均进行相同的预处理。
实施例1
按质量比1：4分别称取预处理后的煤炭与磷酸，加水稀释超声混合，具体的超声参数为25Hz(5min),33Hz(10min),40Hz(5min),59Hz(10min),总时间0.5h，之后烘干转移至管式炉中，在氮气气氛下以3℃min –1的升温速率于900℃碳化1h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到磷掺杂碳P 4C-900；按质量比1：4：2分别称取磷掺杂碳、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下以3℃min –1的升温速率于900℃碳化2h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料P 4N 4C-900。
实施例2
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下以3℃min –1的升温速率于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳N 4C-900；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合，具体的超声参数为25Hz(5min),33Hz(10min),40Hz(5min),59Hz(10min),总时间0.5h，后烘干转移至管式炉中，在氮气气氛下以3℃min –1的升温速率于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 4C-900。
实施例3
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下以3℃min –1的升温速率于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳N 4C-900；按质量比1：4分别称取氮掺杂碳与磷酸直接混合后烘干转移至管式炉中，在氮气气氛下以3℃min –1的升温速率于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 4C-900-d。
实施例4
按质量比1：2：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 2P 4C-900。
实施例5
按质量比1：6：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛 下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 6P 4C-900。
实施例6
按质量比1：4：1分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 4C 1-900。
实施例7
按质量比1：4：3分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 4C 3-900。
实施例8
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：3分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 3C-900。
实施例9
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：5分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 5C-900。
实施例10
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于850℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于850℃碳化1h，得到二次碳化产物；将 二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 4C-850。
实施例11
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于950℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于950℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 4C-950。
实施例12
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于1050℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于1050℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料N 4P 4C-1050。
实施例13
按质量比1：4：2分别称取预处理后的其他碳源(煤沥青、煤焦油，石油沥青、石油焦)、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到一系列氮磷掺杂多孔碳材料。
实施例14
按质量比1：4：2分别称取预处理后的煤炭、其他氮掺杂剂(双氰胺、尿素、吡啶、吡咯、苯胺、氨基酸和嘌呤)与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到一系列氮磷掺杂多孔碳材料。
实施例15
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与其他活化剂(氢氧化钠、碳酸氢钾、碳酸氢钠、碳酸钾和碳酸钠)，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与磷酸，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到一系列氮磷掺杂多孔碳材料。
实施例16
按质量比1：4：2分别称取预处理后的煤炭、三聚氰胺与氢氧化钾，研磨混匀后转移至管式炉中，在氮气气氛下于900℃碳化2h，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；按质量比1：4分别称取氮掺杂碳与其他磷掺杂剂(三苯基膦、植酸、红磷，黑磷、磷酸二氢钾，磷酸二氢钾、磷酸氢二钠、磷酸二氢钠、磷酸镁、磷酸钙、磷酸二氢氨与磷酸氢二氨)，加水稀释超声混合后烘干转移至管式炉中，在氮气气氛下于900℃碳化1h，得到二次碳化产物；将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到一系列氮磷掺杂多孔碳材料。
上述仅为本发明的部分优选实施例，本发明并不仅限于实施例的内容。对于本领域的技术人员来说，在本发明技术方案的构思范围内可以有各种变化和更改，所做的任何变化和更改，均在本发明保护范围内。
对比实施例1
以磨碎的生物质为原料，在500℃炭化1h，冷却后获得预炭化料；将氢氧化钾,碳酸氢钾和预炭化料按质量比2：1：1混合，并按5％的氮元素掺杂量掺杂三聚氰胺，混合后加入去离子水在80℃下水浴浸渍并烘干获得氮掺杂炭；在氮气气氛下800℃活化2.67h冷却后取出研磨；再将5％的亚磷酸钠置于管式炉上游，将上一步获得的氮掺杂炭放于下游，300℃反应2h，冷却至室温取出研磨并酸洗-水洗至中性，烘干获得生物质基氮磷掺杂炭1。
对比实施例2
将6mmol三聚氰胺、910μL植酸和10mL去离子水在室温下混匀，得到水凝胶并冷冻干燥得到白色粉末，在氩气气氛下以2℃min –1的升温速率在1000℃炭化2h，获得氮磷掺杂炭2。
对比实施例3
在氮气气氛下800℃煅烧2g植酸钾1h，升温速率3℃min –1,自然冷却后用盐酸常温处理18h并用去离子水水洗至中性烘干沉淀物获得磷掺杂炭；再取0.1g的磷掺杂炭与2g三聚氰胺研磨混合后高温1000℃热处理2h，用水洗涤、离心并烘干获得氮磷掺杂炭3。
将实施例1-16和对比实施例1-3中获得的氮磷掺杂多孔碳材料按照如下方案进行表征与测试。
1)SEM测试
实施例2制得的代表性的氮磷掺杂多孔碳材料N 4P 4C-900在低分辨率扫描电子显微镜(SEM)下表现出大量分散的粗糙碳,如图1所示，这能够提供丰富的比表面积和孔隙结构，进一步地高分辨率SEM显示，如图2所示，可以看到该碳材料的片层很薄，具有不同的层次化边缘，并且不同的碳之间有一定程度的交联，这种结构利于电子转移和相关物质传输。
2)TEM测试
对N 4P 4C-900进行透射电子显微镜(TEM)测试，如图3所示。高倍TEM图显示了材料具有散乱的晶格条纹，并且可以观察到边缘处由更薄的几层组成，这代表了材料主导的无序化特征，并且伴随着局部的石墨化程度。同时，错乱的晶格之间存在着丰富的缺陷位点。第一步三聚氰胺和氢氧化钾共同作用的氮掺杂过程和第二步的磷酸刻蚀过程都会创造一定的孔隙，并且第二步的磷酸在高温下能够刻蚀碳使其更薄，边缘位点更多，这利于后续的催化过程 的电解液和氧气的可及性。第二步磷酸的刻蚀会脱除部分氮原子并且造成碳的晶格重塑以及引入掺杂磷原子，因此带来相应地内部空位缺陷、拓扑缺陷以及边缘缺陷，形成更多的催化活性位点。
3)X射线衍射(XRD)测试
图4为N 4P 4C-900材料的XRD测试图，材料在24.1°和41.6°左右出现了两个特征峰,分别归因于石墨碳的(002)和(101)面。这说明N 4P 4C-900具有很大的无序化程度，间接证明了材料具有大量的孔隙。这都有利于电解液离子的浸润以及相关物种的传输。
4)拉曼测试
对P 4N 4C-900和N 4P 4C-900进行了拉曼光谱测试，如图5所示。这两种材料在1338cm –1与1586cm –1左右展现出两个强峰，分别为D能带和G能带，D能带代表了材料的无序化/缺陷程度，G能带代表了材料的石墨化程度。I D/I G的值反映了碳材料的无序化/石墨化程度，P 4N 4C-900和N 4P 4C-900的I D/I G分别为0.984和0.988，说明这两类碳材料都具有无序化与石墨化并存的结构。并且氮/磷原子的两步掺杂过程给这两类材料带来了一定的缺陷程度。
5)X射线光电子能谱测试
使用X射线光电子能谱(XPS)分析仪对实施例1和2中的样品进行材料表面元素及含量测试。P 4N 4C-900和N 4P 4C-900都具有较高的碳含量以及一些氧、氮、磷含量。图6为P 4N 4C-900和N 4P 4C-900的高分辨氮分峰图，P 4N 4C-900和N 4P 4C-900分别含有2.0％和2.64％的氮原子，经分峰计算，P 4N 4C-900的吡啶氮(N-6)、吡咯氮(N-5)、石墨氮(N-Q)和氧化氮(N-O)的比例分别为21.6％、18.6％、37.0％以及22.8％；N 4P 4C-900的吡啶氮、吡咯氮、石墨氮和氧化氮的比例分别为15.3％、26.2％、41.8％以及16.7％，如图7所示。图8为P 4N 4C-900和N 4P 4C-900的高分辨磷分峰图，经分峰计算，P 4N 4C-900拥有0.49％的磷含量，包括55.6％的P-C键和44.4％的P-O键；而N 4P 4C-900拥有2.42％的磷含量，包括70.2％的P-C键和29.8％的P-O键。可以看出N 4P 4C-900比P 4N 4C-900拥有更多的氮含量和磷含量，并且N 4P 4C-900的石墨氮和磷碳键的比例更加突出。通过实施例1的方法制得的P 4N 4C-900的氮和磷含量分别为2.0％和0.5％，并且石墨氮/吡啶氮的比值为1.71，P-C键与P-O键的比值为1.25；较P 4C-900增加了一些氮含量而减少了很多磷含量。通过实施例2的方法制得的N 4P 4C-900的氮和磷含量分别为2.64％和2.42％，并且石墨氮/吡啶氮的比值为2.72，P-C键与P-O键的比值为2.35；较N 4C-900减少了一些氮含量而补充了很多磷含量，杂原子掺杂含量和类型精确可控。石墨氮和P-C键可以改变毗邻碳的电荷密度和自旋密度，在氧还原电催化中充当了活性物种的作用，吡啶氮也可以起到协同作用，与氧有关的功能团能够提高材料的润湿性。另外，石墨氮物种也有利于碳材料的电导性。
6)氮气物理吸附测试
使用氮气物理吸附仪对实施例1和2中的样品进行材料比表面积与孔隙结构测试。图9是P 4N 4C-900和N 4P 4C-900的氮气吸/脱附图，两种材料都是典型的微孔材料，在接近0时的低压范围内曲线接近竖直的趋势也印证了材料存在大量微孔。通过测试得出，P 4N 4C-900和N 4P 4C-900的比表面积分别为1220.7和845.5m 2g –1；孔容分别为1.135和0.594cm 3g –1。P 4N 4C-900拥有503.2m 2g –1的微孔和717.5m 2g –1的中孔，较P 4C-900的比表面积866.2m 2g –1又进一步提高，微孔比表面积减少而中孔比表面积大大提升。N 4P 4C-900拥有661.8m 2g –1的微孔和183.7m 2 g –1的中孔，较N 4C-900的比表面积629.8m 2g –1有了显著提高，微孔和中孔比表面积都增加并且中孔比表面积增加一倍左右，如图10所示，证明了P 4N 4C-900和N 4P 4C-900的比表面积具有良好的变化可控性。经过DFT模型分析得出P 4N 4C-900和N 4P 4C-900的孔径分布曲线图11，P 4N 4C-900样品孔径分布分别集中在0.50、0.85以及3.14nm，N 4P 4C-900样品孔径分布分别集中在0.52、0.83和2.71nm,通过实施例1和2制得的材料孔径可控性很好。可以看出，P 4N 4C-900和N 4P 4C-900都具有较大孔径尺寸的微孔与一定比例的中孔，微孔可以为催化反应提供实际反应场所，中孔能够方便传质与相关物质的转移，微孔和中孔的协同作用得以使更多的活性位点的作用发挥出来，保证了优异的催化效率。
7)碱性催化性能测试
工作电极的制备过程如下：称取制备的氮磷掺杂多孔碳材料3-5mg放入离心管，然后加入80-160μL异丙醇、160-320μL水与10-20μL的全氟磺酸-聚四氟乙烯共聚物配制成250-500μL悬浊液超声30min，形成分散良好的黑色粘液，然后取5-15μL粘液滴于玻碳电极上晾干制备成工作电极，以Ag/AgCl电极为参比电极，以铂丝为对电极在工作站上进行氧还原电催化性能测试。相似地，将20％Pt/C按照上述制备方法制成黑色粘液并且滴于玻碳电极上晾干进行测试，并与本发明制备的材料进行性能比较，其中，Pt/C催化剂在玻碳电极上的负载量保持在100μg cm –2左右。
在恒温水浴25℃条件下0.1mol L –1的KOH溶液中对实施例2的样品N 4P 4C-900以及20％Pt/C进行CV、LSV、RRDE测试，循环稳定性与抗甲醇和小分子测试以及碱性锌空电池测试。如图12-21所示。
由图12可以看出，N 4P 4C-900在N 2中表现出近似矩形的电化学特征，归因于材料的电容特性；在O 2中具有较优的氧化还原峰，峰电位为0.872V vs.RHE，显示出制备的电极材料较好的催化潜力。由图13可以看出，N 4P 4C-900不同转速下的LSV曲线，随着转速的提高，电流密度均匀增加。在高电位区时材料表现出较好的催化电位，来源于动力学控制；在低电位区时材料表现出较好的电流密度，来源于氧气扩散控制。由图14可以看出，N 4P 4C-900表现出优于20％Pt/C的起始电位与半波电位，这也是优于P 4N 4C-900的。N 4P 4C-900在标准RHE电位下起始电位为0.97V，半波电位为0.85V，极限电流密度为6.36mA cm –2。此外，图15表明通过变频超声混合法制得的N 4P 4C-900比通过直接混合制得的N 4P 4C-900-d具有显著更好的性能，突出了本专利开发的变频超声混合法对于制得的材料的性质和电化学表现的重要性！由图16可以看出，RRDE测试与计算表明，在0.3-0.9V vs.RHE电位下，N 4P 4C-900过氧化氢产率低于2.13％，电子转移数高于3.96，与Pt/C表现相当，印证了N 4P 4C-900氧还原电催化过程经历了一个主导的四电子路径。N 4P 4C-900在碱性条件下优异的催化性能得益于由先氮掺杂后磷刻蚀的两步热解法带来的充足的氮磷相关的活性位点以及用于传质的联通微孔-中孔结构。
将实例2中的N 4P 4C-900在0.1mol L –1KOH电解液中400rpm转速下进行i-t计时电流法测试，同时20％Pt/C在同样的条件下进行测试做对比，如图17所示。N 4P 4C-900在30000s的循环后电流保持率为95.45％，远高于20％Pt/C的稳定性68.40％。将实例2中的N 4P 4C-900和20％Pt/C在0.1mol L –1KOH电解液中进行抗甲醇测试，如图18所示。通过i-t计时电流法测试，在测试200s时加入甲醇，N 4P 4C-900的催化活性基本保持不变，而Pt/C催化剂发生了明显的甲醇氧化反应。将实例2中的N 4P 4C-900在0.1mol L –1KOH电解液中进行抗有机小分子(NaNO 2和 NaHSO 3)测试，如图19，分别在电解液中加入NaNO 2和NaHSO 3后，N 4P 4C-900均保持较稳定的催化性能，并且更换为新鲜电解液后催化性能基本可完全恢复。说明该发明制备的氮磷共掺杂碳材料在碱性条件下具有优秀的循环稳定性与抗甲醇和小分子性能。这得益于材料稳定的活性位点和孔隙结构。将N 4P 4C-900作为阴极催化剂应用于碱性锌空气电池，电池最大功率密度可达223.2mW cm –2,如图20。另外，该电池可以在不同的电流密度下长时间稳定放电，并且具有良好的电化学反应可逆性，如图21。N 4P 4C-900展示出了在碱性燃料电池和金属空气电池上的较大的应用潜力。
8)酸性催化性能测试
在0.5mol L –1H 2SO 4溶液中对实施例2的样品N 4P 4C-900以及20％Pt/C进行LSV测试。如图22所示。N 4P 4C-900表现出优于20％Pt/C的半波电位与极限电流密度，并且这明显优于P 4N 4C-900。N 4P 4C-900在标准RHE电位下起始电位为0.82V，半波电位为0.65V，极限电流密度为6.48mA cm –2。这说明在酸性条件下N 4P 4C-900材料依然具有优秀的催化效果。N 4P 4C-900在酸性条件下优异的催化性能得益于由两步顺序掺杂法获得的高比例的石墨氮与磷碳键物种以及丰富的缺陷。
9)中性催化性能测试
在0.1mol L –1PBS(pH＝7)溶液中对实施例2的样品N 4P 4C-900以及20％Pt/C进行LSV测试。如图23所示。N 4P 4C-900表现出优于20％Pt/C的半波电位与极限电流密度，这也是明显优于P 4N 4C-900的。N 4P 4C-900在标准RHE电位下起始电位为0.87V，半波电位为0.67V，极限电流密度为7.12mA cm –2。这说明材料具有应用到生物燃料电池的较大潜力。N 4P 4C-900在中性条件下优异的催化性能得益于由两步顺序掺杂法获得的氮磷掺杂位点以及适宜中性离子发挥作用的丰富的缺陷和孔隙结构。
10)对比实施例样品的催化性能测试
根据对比实施例1获得氮磷掺杂炭1，如专利CN107610945A所述，可以作为超级电容器电极材料。但经过ORR电催化测试，如图24，代表性的氮磷掺杂炭1在碱性条件0.1M KOH电解液中的电催化性能比较差，不具有作为燃料电池阴极催化剂应用的潜质。这也突出了本发明实施例1和2的方法对于获得宽pH值范围内可用的氧还原催化剂的重要性。
根据对比实施例2获得氮磷掺杂炭2，如专利CN105762376A所述，可以在碱性条件0.1M KOH电解液中具有一定的电催化活性。但经过酸性和中性条件下的ORR电催化测试，如图25和26，代表性的氮磷掺杂炭2在0.5M H 2SO 4和0.1M PBS(pH＝7.0)的电催化性能比较差，不具有作为质子交换膜燃料电池和微生物燃料电池阴极催化剂应用的潜质。这也突出了本发明实施例1和2的方法对于获得宽pH值范围内可用的氧还原催化剂的重要性。
同样的，根据对比实施例3获得氮磷掺杂炭3，如专利CN107661772B所述，可以在碱性条件0.1M KOH电解液中具有一定的电催化活性。但本专利未提及酸性和中性条件下材料的ORR电催化性能，说明代表性的氮磷掺杂炭3在酸性和中性电解液中电催化性能不足，不具有在酸性和中性条件中作为阴极催化剂应用的潜质。这也突出了本发明实施例1和2的方法对于获得宽pH值范围内可用的氧还原催化剂的重要性。

Claims (8)

  1. 宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，其特征在于，包括以下步骤：
    (1)将天然矿物基碳源清洗晾干，然后混合球磨；保护气体下预碳化；将炭化料在80-90℃条件下用2-3mol L –1氢氧化钾溶液碱洗1-3h，过滤，水洗至滤液呈中性；再在50-60℃条件下用4-6mol L –1盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，产物烘干；
    (2)按质量比1：2-6：1-3分别称取前一步的待掺杂碳、氮掺杂剂与活化剂，研磨混匀后转移至管式炉中，在氮气气氛下于850-1050℃碳化1-4h，升温速率为2-20℃ min –1，碳化结束后取出，经酸洗、过滤、水洗、烘干得到氮掺杂碳；
    (3)按质量比1：3-5分别称取前一步的待掺杂碳与磷掺杂剂，加水稀释混合，之后烘干转移至管式炉中，在氮气气氛下于850-1050℃碳化1-4h，升温速率为2-20℃ min –1，经酸洗、过滤、水洗、烘干得到磷掺杂碳；
    所述的方法按照(1)(2)(3)或者(1)(3)(2)的步骤将二次碳化产物在40-60℃条件下用1mol L –1稀盐酸溶液酸洗1-3h，过滤，水洗至滤液呈中性，干燥后得到氮磷掺杂多孔碳材料。
  2. 根据权利要求1所述宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，其中，通过按照(1)(2)(3)步骤制得的氮磷掺杂多孔碳N 4P 4C-900比表面积为845.5m 2g –1，微孔为661.8m 2g –1，中孔为183.7m 2g –1；氮磷含量分别为2.64％和2.42％，石墨氮/吡啶氮的比值为2.72，磷碳键与磷氧键的比值为2.35。
  3. 根据权利要求1所述宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，其中，通过(1)(3)(2)步骤制得的氮磷掺杂多孔碳P 4N 4C-900比表面积为1220.7m 2g –1，微孔为503.2m 2g –1，中孔为717.5m 2g –1；氮磷含量分别为2.0％和0.5％，石墨氮/吡啶氮的比值为1.71，磷碳键与磷氧键的比值为1.25。
  4. 根据权利要求1所述宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，其特征在于，步骤(3)中，混合方法为超声混合，超声时间为0.5-3h，变频超声频率为25-60Hz。
  5. 根据权利要求1所述宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，其特征在于，步骤(1)中所述天然矿物基碳源为煤炭、煤沥青、煤焦油、煤焦油沥青，石油沥青、石油焦的一种或几种。
  6. 根据权利要求1所述宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，其特征在于，步骤(1)中的预碳化温度为600-1000℃，氮气气氛下碳化2h，升温速率为5℃ min –1。
  7. 根据权利要求1所述宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，其特征在于，步骤(2)中，所述氮掺杂剂为三聚氰胺、双氰胺、尿素、吡啶、吡咯、苯胺、氨基酸和嘌呤中的一种或多种；所述活化剂为氢氧化钾、氢氧化钠、碳酸氢钾、碳酸氢钠、碳酸钾和碳酸钠的一种或多种。
  8. 根据权利要求1所述宽pH范围氧还原电催化用氮磷掺杂多孔碳材料的制备方法，其特征在于，步骤(3)中，所述磷掺杂剂为磷酸、三苯基膦、植酸、红磷、黑磷、磷酸氢二钾、磷酸二氢钾、磷酸氢二钠、磷酸二氢钠、磷酸镁、磷酸钙、磷酸二氢氨与磷酸氢二氨中的一种或多种。
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