Nitrogen and phosphorus co-doped crystalline carbon materials

Abstract

The nitrogen and phosphorus co-doped crystalline carbon materials are prepared by a template-free method that includes pyrolizing a precursor mixture including a carbon source, a nitrogen source, and a phosphorus source. The method involves mixing known amounts of the precursor components, dissolving the precursor mixture in deionized water, distilling solvent from the aqueous mixture, and vacuum drying the residue to a dry solid mixture. The mixture is then carbonized by pyrolysis at 900 C. in an argon atmosphere to obtain a nitrogen and phosphorus co-doped crystalline carbon material. The principles of the method are illustrated by a precursor mixture of sucrose, urea, and ammonium dihydrogen phosphate (NH.sub.4H.sub.2PO.sub.4). The amount of ammonium salt in the precursor mixture plays a key role in controlling the crystallinity, morphology, and composition of the N/P co-doped crystalline carbon material.

Claims

1. A method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials, comprising the step of pyrolizing a template-free precursor mixture containing a carbon source, a nitrogen source, and a phosphorus source at 900 C. in an argon atmosphere, wherein the carbon source comprises at least one carbon source selected from the group consisting of carbohydrates, hydrocarbon-based polymers, organic dyes, organic salts, organic wastes, and hydrocarbons.

2. The method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials of claim 1, wherein the nitrogen source comprises at least one nitrogen source selected from the group consisting of urea, thiourea, guanidine, and nucleic bases.

3. The method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials of claim 1, wherein the phosphorus source comprises at least one phosphorus source selected from the group consisting of ammonium dihydrogen phosphate, diammonium phosphate, ammonium hypophosphite, alkylammonium phosphates.

4. The method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials of claim 1, further comprising the steps of, prior to said pyrolizing step: mixing the sources in the precursor mixture; providing deionized water to act as a solvent; dissolving the precursor mixture in the deionized water to form an aqueous mixture; distilling the solvent from the aqueous mixture; and vacuum drying residue from the distilling step to a dry, solid precursor mixture.

5. A nitrogen and phosphorus co-doped crystalline carbon material prepared according to the method of claim 4.

6. The method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials according to claim 1, wherein: said carbon source comprises sucrose; said nitrogen source comprises urea; and said phosphorus source comprises ammonium dihydrogen phosphate.

7. A nitrogen and phosphorus co-doped crystalline carbon material prepared according to the method of claim 6.

8. The method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials according to claim 6, further comprising the steps of, prior to said pyrolizing step: mixing the sources in the precursor mixture; providing deionized water to act as a solvent; dissolving the precursor mixture in the deionized water to form an aqueous mixture; distilling the solvent from the aqueous mixture; and vacuum drying residue from the distilling step to a dry, solid precursor mixture.

9. A nitrogen and phosphorus co-doped crystalline carbon material prepared according to the method of claim 8.

10. The method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials according to claim 8, wherein the precursor mixture has a urea-to-ammonium dihydrogen phosphate mass ratio of 1:3.

11. A method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials, comprising the step of pyrolizing a template-free precursor mixture containing a carbon source, a nitrogen source, and a phosphorus source at 900 C. in an argon atmosphere, wherein the phosphorus source comprises at least one phosphorus source selected from the group consisting of ammonium dihydrogen phosphate, diammonium phosphate, ammonium hypophosphite, alkylammonium phosphates.

12. A method for synthesizing nitrogen and phosphorus co-doped crystalline carbon materials, comprising the step of pyrolizing a template-free precursor mixture containing a carbon source, a nitrogen source, and a phosphorus source at 900 C. in an argon atmosphere, wherein the carbon source comprises sucrose; the nitrogen source comprises urea; and the phosphorus source comprises ammonium dihydrogen phosphate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the X-Ray Diffraction (XRD) patterns of three samples of nitrogen and phosphorus co-doped crystalline carbon materials prepared with different urea to phosphate ratios, namely, N/P-C1-900 (3:1 ratio), N/P-C2-900 (1:1 ratio), and N/P-C3-900 (1:3 ratio).

(2) FIG. 2A is a plot showing a Brunauer-Emmett-Teller (BET) characterization of N.sub.2 adsorption-desorption isotherms for N/P-C1-900, N/P-C2-900, and N/P-C3-900.

(3) FIG. 2B is a [plot showing Barrett-Joyner-Halenda (BHJ) pore size distribution for N/P-C1-900, N/P-C2-900, and N/P-C3-900.

(4) FIGS. 3A, 3B, and 3C show Field Emission Scanning Electron Microscopy (FESEM) micrographs of sample N/P-C1-900 at 1 m with magnifications of 5,000, 10,000, and 7,500, respectively.

(5) FIG. 3D shows an FESEM micrograph of sample N/P-C1-900 at 100 nm with magnification of 30,000.

(6) FIGS. 4A and 4B show FESEM micrographs of sample N/P-C2-900 at 1 m with magnifications of 5,000 and 3,000, respectively.

(7) FIGS. 5A, 5B, and 5C show FESEM micrographs of sample N/P-C3-900 at 1 m with magnifications of 10,000, 5,000, and 10,000, respectively.

(8) FIG. 5D shows an FESEM micrograph of sample N/P-C3-900 at 100 nm with magnification of 30,000.

(9) FIG. 6A is a comparison of X-ray Photoelectron Spectroscopy (XPS) survey spectra of samples N/P-C1-900, N/P-C2-900, and N/P-C3-900.

(10) FIGS. 6B, 6C, and 6D are high resolution XPS spectra of the deconvoluted and fitted N.sub.1s component in the XPS spectra of samples N/P-C1-900, N/P-C2-900, and N/P-C3-900, respectively.

(11) FIGS. 7A, 7B, and 7C are high resolution XPS spectra of the deconvoluted and fitted P.sub.2p component in the XPS spectra of samples N/P-C1-900, N/P-C2-900, and N/P-C3-900, respectively.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(12) Reference will now be made in detail to embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings. The nitrogen and phosphorus co-doped crystalline carbon materials are prepared by a template-free method that includes pyrolizing a precursor mixture including a carbon source, a nitrogen source, and a phosphorus source. The method involves mixing known amounts of the precursor components, dissolving the precursor mixture in deionized water, distilling solvent from the aqueous mixture, and vacuum drying the residue to a dry solid mixture. The mixture is then carbonized by pyrolysis at 900 C. in an argon atmosphere to obtain a nitrogen and phosphorus co-doped crystalline carbon material. The principles of the method are illustrated by a precursor mixture of sucrose, urea, and ammonium dihydrogen phosphate (NH.sub.4H.sub.2PO.sub.4). The amount of ammonium salt in the precursor mixture plays a key role in controlling the crystallinity, morphology, and composition of the N/P co-doped crystalline carbon material. The absence of a hard template (such as silica) or a soft template (eutectic mixture of metal salts) in the synthesis leaves the crystalline carbon material product relatively free of impurities that might otherwise affect the structure and/or electronic properties of the carbon materials.

(13) For purposes of this disclosure, co-doped refers to materials doped with at least two heteroatoms, such as, e.g., nitrogen, oxygen, sulfur, phosphorus, chlorine, bromine, and iodine. The term nitrogen and phosphorus is used interchangeably with N/P. The term ammonium dihydrogen phosphate is used interchangeably with NH.sub.4H.sub.2PO.sub.4.

(14) The carbon source of the precursor moisture includes at least one carbon source selected from carbohydrates (e.g., sugar, starch, guar gum, acacia gum, etc.), hydrocarbon-based polymers (e.g., PVA, PBI, PS, polythiophenes, etc.), organic dyes (e.g., murexide, methylene blue, methylene red, etc.), organic salts (e.g., EDTA, protic organic ionic salts, aprotic organic ionic salts, etc.), organic wastes (e.g., feathers, hairs, etc.), and hydrocarbons (e.g., wax, etc.). The nitrogen source may be a nitrogen-containing organic or inorganic salt, including urea, thiourea, guanidine, nucleic bases, etc. The phosphorus source can be an ammonium-based, phosphorus-containing organic or inorganic salt, including ammonium dihydrogen phosphate, diammonium phosphate, ammonium hypophosphite, alkylammonium phosphates, etc. The examples described herein employed a precursor mixture of sucrose, urea, and ammonium dihydrogen phosphate. However, the present inventors anticipate that precursor mixtures containing any combination of the carbon, nitrogen, and phosphorus sources described above should produce crystalline carbon materials having similar properties when processed according to the steps of the present method.

Example 1

Synthesis of N/P Co-Doped Crystalline Carbon Material

(15) Briefly, a mixture containing known amounts of sucrose, urea, and ammonium dihydrogen phosphate (NH.sub.4H.sub.2PO.sub.4) were first dissolved in deionized water, followed by distillation of the solvent, and vacuum drying the residue overnight to obtain a dry solid mixture. By varying the mass ratio of NH.sub.4H.sub.2PO.sub.4 to urea, e.g., (1:3), (1:1) and (3:1), while keeping the amount of carbon precursor (sucrose) the same, three different starting mixtures, (N/P-C1-900, N/P-C2-900 and N/P-C3-900) were prepared. Specifically, N/P-C1-900, N/P-C2-900, and N/P-C3-900 are samples with varying the mass ratios of NH.sub.4H.sub.2PO.sub.4 to urea having ratios of (1:3), (1:1), and (3:1), respectively. Each of these mixtures was subject to pyrolysis by carbonizing the precursor at 900 C. in an argon (Ar) environment to obtain the corresponding nitrogen and phosphorus co-doped crystalline carbon materials. The choice of temperature (900 C.) for synthesis of the carbon materials was based on the previous findings of several research studies, which reveal that the product heteroatom doped carbon materials retain high percentage of dopant, as well as achieved high surface area, at this temperature.

(16) Apart from sucrose, which can be used as a carbon precursor for synthesizing the exemplary heteroatom co-doped carbon materials, urea was used to dope nitrogen in the final product (N/P co-doped carbon materials). Similarly, the primary purpose of using the NH.sub.4H.sub.2PO.sub.4 was to dope both nitrogen and phosphorus in the carbon structure.

Example 2

XRD Analysis of N/P Co-Doped Crystalline Carbon Material

(17) FIG. 1 shows the XRD patterns of the nitrogen and phosphorus co-doped carbon materials synthesized according to Example 1. The XRD studies of the synthesized N/P co-doped carbon materials (N/P-C1-900, N/P-C2-900 and N/P-C3-900) were carried out to validate the formation of graphitic phases due to carbonization at high temperature, and also to observe the amount of disordered phases created by the heteroatom (N/P) doping. Further, the XRD patterns show the effect of the additive composition (ratio of NH.sub.4H.sub.2PO.sub.4 to urea) on the structural alterations in the synthesized N/P co-doped carbon materials. Unlike most heteroatom-doped carbon materials, which exhibit a broad XRD peak (representing highly amorphous carbon phases), the presently synthesized N/P co-doped carbon materials contain a number of sharp XRD peaks, which exhibit the presence of various crystalline phases of carbon. The XRD patterns of the present N/P co-doped carbon materials are very different from the nitrogen-doped, sulfur-doped, nitrogen/phosphorus co-doped, or nitrogen/sulfur co-doped carbon materials previously discovered.

(18) In particular, FIG. 1 shows the XRD pattern for N/P-C1-900 has one broad diffuse band centered around 23 at Bragg angle 2, and one relatively less broad band with a superimposed peak ca. 43.8 2, which are associated with the (002) and (100) lattice planes of a typical less ordered and/or Turbostratic carbon (T-Carbon), respectively. The T-carbon is generally regarded as an analogue of the hexagonal carbon (H-Carbon) with loosely ordered structure, often representing the amorphous form of the graphitic carbon. By varying the mass ratio of urea to NH.sub.4H.sub.2PO.sub.4, (3:1) in N/P-C1-900, (1:1) in N/P-C2-900 and (1:3) in N/P-C3-900, a gradual flattening of the broad 23 2 peak was observed with increasing amount of NH.sub.4H.sub.2PO.sub.4 in the starting precursor mixture for synthesizing the N/P co-doped carbon materials. In particular, the XRD pattern of N/P-C3-900 shows peaks (26 and 28 2), which can be ascribed to fragmented microcrystallites having relatively more ordered structure. This indicates increasing the concentration of NH.sub.4H.sub.2PO.sub.4 can develop more crystalline phases in the N/P co-doped carbon materials.

(19) Further, FIG. 1 also shows that the XRD pattern for the N/P-C1-900 sample has some new XRD peaks ca. 30, 30.8, 35.5 and 40, which were not observed or reported for other heteroatom-doped carbon materials. While investigating the origin of these new XRD peaks, it was found that the XRD patterns of the soot obtained from the detonation of TNT/diesel oil revealed the presence of amorphous carbon and several crystalline carbon phases. In particular, it was found that a sharp diffraction peak ca. 30 in the XRD pattern of the detonation soot could not be assigned to any known carbon allotropes, such as graphite, diamond, or fullerenes. This sharp XRD peak was also observed in fullerene soot and chimney soot, but remained unidentified until recently when researchers discovered a new carbon allotrope with six-fold helical chains in all, having alternating single and double bonds containing sp.sup.2 bonding networks, which provided an excellent match to this previously unidentified carbon phase with a sharp diffraction peak ca. 30. This new carbon phase has a 6-atom rhombohedral primitive unit cell, and thus is termed as rh6 carbon.

(20) FIG. 1 also shows that the XRD patterns of the N/P co-doped materials (N/P-C1-900, N/P-C2-900, and N/P-C3-900) display a prominent XRD peak ca. 30 2, which can be ascribed to the (101) plane of the rh6 carbon phase. The XRD patterns of these materials also show another concomitant XRD peak with relatively lower intensity ca. 40 2, which is also characteristic to this carbon phase. The XRD patterns shown in FIG. 1 exhibit a clear trend of increasing intensity of rh6 diffraction peaks when going from N/P-C1-900.fwdarw.N/P-C2-900.fwdarw.N/P-C3-900. This indicates that the ratio of additives (Urea/NH.sub.4H.sub.2PO.sub.4) has a significant effect on the formation of crystalline phases in these novel N/P co-doped catalyst materials. In fact, N/P-C3-900, which was prepared by the carbonization of a mixture containing Urea/NH.sub.4H.sub.2PO.sub.4, (1:3) in carbon precursor (sugar), achieved more crystalline phases than the N/P-C1-900 and N/P-C2-900 catalyst materials.

(21) FIG. 1 shows another XRD peak ca. 30.8 2 on the shoulder of rh6 carbon, which was common in all of the N/P co-doped carbon materials. This peak corresponds to the relatively less stable sp.sup.2 hybridized carbon having three-dimensional (3D) crystal structure (K4). Although the K4 carbon is dynamically unstable, it still shows structural stability on the potential energy surface and exhibits excellent metallic properties. The XRD patterns of all of the N/P co-doped carbon materials show another common peak ca. 35.5 2, which best matches with the diffraction peak of body-centered tetragonal carbon, termed as bct-C4. In contrast to all sp.sup.2 carbon phases (T-carbon, rh6, and K4), the bct-C4 is a form of crystalline sp.sup.3 carbon, and its structure seems to be an intermediate between graphite and hexagonal carbon.

(22) The XRD studies of N/P-C1-900, N/P-C2-900 and N/P-C3-900 revealed the presence of four different carbon phases in the newly synthesized N/P co-doped carbon materials. Specifically, the comparison of the diffraction patterns of these carbon materials indicates that the higher concentration of NH.sub.4H.sub.2PO.sub.4 in the starting precursor mixture induced more crystalline phases in these N/P co-doped carbon materials.

Example 3

Surface Area Analysis of N/P Co-Doped Crystalline Carbon Material

(23) FIG. 2A shows the BET characterization of N.sub.2 adsorption-desorption isotherms for N/P-C1-900, N/P-C2-900, and N/P-C3-900. The shape of all three isotherms are similar to Type IV (according to IUPAC classifications) with clear hysteresis loops extending from P/P0=0.8 to ca. 0.99, indicating the coexistence of mesopores (pore diameter <50 nm) and macropores (pore diameter >50 nm) in these materials. The BET specific surface areas (SBET) of N/P-C1-900, N/P-C2-900 and N/P-C3-900 were found to be 74, 117 and 29 m.sup.2g.sup.1, respectively. Since, all the samples were heated at the same pyrolysis temperature (900 C.), the differences in the SBET of the obtained N/P co-doped carbon materials indicate that the mass ratio of urea to NH.sub.4H.sub.2PO.sub.4 in the starting mixture may have resulted in varying surface areas exhibited by these materials.

(24) The distribution of different pore sizes in these carbon materials was investigated from the BJH pore size distribution (PSD) curves shown in FIG. 2B. The PSD curves for N/P-C1-900 and N/P-C2-900 showed a peak around 68 nm, indicating similar pore diameter distribution and the presence of macropores in these two carbon materials. In contrast, the PSD curve for N/P-C3-900 in FIG. 2B did not show any prominent peak and was unable to provide any information about the pore size distribution in this carbon material.

Example 4

Morphological Analysis of N/P Co-Doped Crystalline Carbon Material

(25) The surface features/morphology of the synthesized N/P co-doped carbon materials were investigated using field emission scanning electron microscopy (FESEM). FIGS. 3A-3D, 4A-4B, and 5A-5D show the FESEM images of the N/P-C1-900, N/P-C2-900 and N/P-C3-900 materials, respectively. In particular, the FESEM images of N/P-C1-900 (shown in FIGS. 3A-3D) and N/P-C2-900 (shown in FIGS. 4A-4B) exhibit morphological patterns that include solid log/rod like microstructures and uneven/irregular shaped particles embedded on the rods. A closer look at FESEM image of N/P-C1-900 in FIG. 3A reveals different varieties of the microstructured carbon rods with: a sliced structure (1); open edges (1, 2, 3, and 4); different sizes; and displaying both smooth (3) and wrinkled surfaces (2). In particular, FIG. 3B shows a rod like structure with a uniform diameter of 7.50 m, while FIG. 3C shows a microstructured rod having non-uniform diameter (thin part 2.4 m) with a wrinkled surface. The high magnification FESEM image of N/P-C1-900 shown in FIG. 3D shows a carbon rod having diameter in the range of 200-300 nm, while a carbon rod with a much larger diameter can also be seen in the rear.

(26) The morphological patterns of sample N/P-C2-900 are shown in FIGS. 4A and 4B. Specifically, FIGS. 4A and 4B show some resemblance to the structures shown by the N/P-C1-900 sample in FIGS. 3A-3D, with broken structures and microstructured rods. For example, FIG. 4B displays a typical non-uniform structured carbon rod having a diameter of about 1.63 and 2.44 m at two different points. It is important to note that the N/P co-doped carbon materials shown herein were synthesized without using any soft or hard templates. Therefore, the morphological patterns displayed by these materials are novel and unique in terms of their originality due to their template free synthesis.

(27) In contrast to N/P-C1-900 and N/P-C2-900, the FESEM images of N/P-C3-900 shown in FIGS. 5A-5D reveal a very different and novel coral-shaped morphology. Specifically, the FESEM image in FIG. 5A shows two major kinds of structures in N/P-C3-900, namely, microstructured flakes and randomly distributed spherically shaped particles. A closer inspection of the spherically shaped cluster in FIGS. 5B-5D show a unique and novel smooth surface, coral shaped morphology. At a higher magnification (10,000), shown in FIG. 5D, small particles in the range of 100-200 nm are randomly distributed on the coral surface.

Example 5

XPS Analysis of N/P Co-Doped Crystalline Carbon Material

(28) FIG. 6A shows the XPS survey spectra of N/P-C1-900, N/P-C2-900, and N/P-C3-900. In FIG. 6A, the typical XPS survey scans for N/P-C1-900, N/P-C2-900, and N/P-C3-900 indicate the presence of peaks corresponding to N.sub.1s, P.sub.2p, C.sub.1s and O.sub.1s in each of these carbon materials. The corresponding amounts of nitrogen, phosphorus, carbon, and oxygen (at %), as determined from the core-level XPS spectra of these sample materials, are provided in Table 1.

(29) TABLE-US-00001 TABLE 1 XPS spectra results Sample ID N.sub.1s (at %) P.sub.2p (at %) C.sub.1s (at %) O.sub.1s (at %) N/P-C1-900 5.04 5.66 70.69 16.72 N/P-C2-900 3.13 4.27 73.06 17.39 N/P-C3-900 3.09 7.58 64.96 22.34

(30) The XPS spectra of these materials show peaks for C (arising mainly from sugar precursor), N (arising mainly from urea precursor), P (arising mainly from NH.sub.4H.sub.2PO.sub.4 precursor) and O (both from sugar and NH.sub.4H.sub.2PO.sub.4 precursors). It has been reported that urea can be successfully used to achieve nitrogen doping in carbon materials (NDCMs). However, the use of an ammonium-based phosphate salt (such as NH.sub.4H.sub.2PO.sub.4) has not been reported to date. From Table 1, it can be clearly seen that the atomic percentage of doped nitrogen content in N/P-C1-900, N/P-C2-900, and N/P-C3-900 subsequently decreased from 5.04% to 3.13% to 3.09%, respectively, in accordance with the decreasing amount of the urea precursor used for synthesizing the N/P co doped carbon materials.

(31) However, upon comparing the atomic percentage of phosphorus content in the N/P co-doped carbon materials, the N/P-C3-900 achieved the highest amount of doped phosphorus (7.58%), since N/P-C3-900 had the highest mass ratio of NH.sub.4H.sub.2PO.sub.4 to urea (3:1) used in the preparation of this carbon material. The atomic percentage of doped phosphorus content in N/P-C1-900 and N/P-C2-900 was 5.66% and 4.27%, respectively, which was not consistent with the mass ratio of NH.sub.4H.sub.2PO.sub.4 to urea used in the preparation of these sample materials. One possible reason behind this inconsistency could be the competing phenomenon of nitrogen doping while annealing at high temperatures, where both the urea precursor and the ammonium ion (NH.sub.4.sup.+) from NH.sub.4H.sub.2PO.sub.4 act as the nitrogen dopant and could compete in doping phosphorus in the dual N/P co-doped carbon systems. Apart from N and P, a consistent increase in the amount of doped oxygen (at %) was also observed in N/P co-doped carbon materials with increasing mass ratio of NH.sub.4H.sub.2PO.sub.4 to urea. Table 1 shows that the atomic percentage of oxygen in N/P-C1-900, N/P-C2-900 and N/P-C3-900 was 16.72%, 17.39 and 22.34%, respectively.

(32) FIGS. 6B-6D show high resolution XPS spectra of the deconvoluted and fitted N.sub.1s component in the XPS spectra of (b) N/P-C1-900, (c) N/P-C2-900, and (d) N/P-C3-900. To identify the types of nitrogen functionalities, the deconvolution of N.sub.1s region in the XPS survey spectra of N/P-C1-900, N/P-C2-900 and N/P-C3-900 was performed and fitted with three component peaks centered at about 398.8 eV, 401.2 eV, and 404 eV. Each of these peaks are attributed to pyridinic-N, quaternary-N (or graphitic-N), and oxidized pyridinic-N (labelled as pyridinic-NO), respectively.

(33) These nitrogen functionalities create different chemical and electronic environments with their neighboring carbon atoms, and therefore play different roles in the electrocatalytic properties of N/P co-doped carbon materials. Previous reports on the development of nitrogen-doped carbon materials for their potential application as an electrocatalyst for oxygen reduction reaction (ORR) reveal that high proportions of the pyridinic-N and quaternary-N in the nitrogen-doped carbon material can be advantageous for the ORR. These two types of nitrogen functionalities not only provide active sites for the ORR, but also provide high stability during long-term catalytic reaction in a fuel cell. More recently, it has been reported that the carbon atoms adjacent to the pyridinic-N display high Lewis basicity, and therefore provide more active sites for ORR.

(34) In this regard, for N/P-C1-900, the deconvoluted N.sub.1s spectrum shown in FIG. 6B reveals that this carbon material achieved a higher proportion of graphitic-N (63.6%) compared to pyridinic-N (35.2%). In addition, a small proportion of pyridinic-NO (1.2%) was also present in this carbon material. In the case of N/P-C2-900, FIG. 6C shows that when compared to the first material (N/P-C1-900), the intensity of the peak corresponding to the graphitic-N decreased significantly (percentage of graphitic-N 44.9%) compared to the pyridinic-N, which increased to 51.1%. Additionally, N/P-C2-900 also exhibited an increase in the proportion of pyridinic-NO (4%), which was relatively small in the case of N/P-C1-900.

(35) Interestingly, the relative proportion of graphitic-N to pyridinic-N continued to increase in the third material, N/P-C3-900. FIG. 6D shows a significantly higher proportion of pyridinic-N (70.8%) to graphitic-N (25.9%) in N/P-C3-900. In addition, the percentage of pyridinic-NO was 3.23% in this material. The atomic percentage values of pyridinic-N, quaternary-N (or graphitic-N), and pyridinic-NO, determined from the deconvolution of N.sub.1s component in the XPS spectra of N/P-C1-900, N/P-C2-900, and N/P-C3-900 are provided in Table 2.

(36) TABLE-US-00002 TABLE 2 Atomic percentage values of pyridinic-N, quaternary-N (or graphitic-N), and pyridinic-NO Pyridinic-N (at Quaternary-N (or Pyridinic-NO Sample ID %) graphitic-N) (at %) (at %) N/P-C1-900 35.2 63.6 1.20 N/P-C2-900 51.1 44.9 4 N/P-C3-900 70.8 25.9 3.23

(37) Previous reports on the development of N and N/P co-doped carbon materials disclose that the quaternary-N is the most stable nitrogen configuration at high temperatures, and its relative proportion compared to pyridinic-N and other nitrogen configurations increases with higher carbonization temperatures. Since all of the carbon materials (N/P-C1-900, N/P-C2-900, and N/P-C3-900) were carbonized at 900 C., the increasing proportion of pyridinic-N compared to quaternary-N from N/P-C1-900.fwdarw.N/P-C2-900.fwdarw.N/P-C3-900 indicates that increasing the mass ratio of NH.sub.4H.sub.2PO.sub.4 to urea in the starting precursor mixture may have a major role in achieving a high proportion of pyridinic-N in these materials. Recently, it has been reported that a high proportion of pyridinic-N and quaternary-N in the nitrogen-doped carbon materials displayed facile Oxygen Evolution Reaction (OER). Hence, the high catalytic activity for OER displayed by the presently synthesized N/P co-doped carbon materials can be attributed to the high proportions of the two types of nitrogen groups. In particular, N/P-C3-900 exhibited the best catalytic activity for OER, and despite having a lower amount of doped nitrogen (3.09%), this may be due to the high proportions of pyridinic-N (70.8%) compared to quaternary-N (25.9%).

(38) FIGS. 7A-7C show high resolution XPS spectra of the deconvoluted and fitted P.sub.2p component in the XPS spectra of (a) N/P-C1-900, (b) N/P-C2-900, and (c) N/P-C3-900. The P.sub.2p spectra of N/P-C1-900, N/P-C2-900, and N/P-C3-900 were deconvoluted and fitted with two different bands centered at 133.4 eV and 134.5 eV, corresponding to the PO and PC bonds, respectively, in these carbon materials. From Table 1, the surface composition analysis reveals that the oxygen content (at. %) increases with increasing P-doping as we go from N/P-C1-900.fwdarw.N/P-C2-900.fwdarw.N/P-C3-900. Moreover, the deconvoluted and fitted P.sub.2p XPS spectra of all of the N/P co-doped carbon materials shown in FIGS. 7A-7C show that the relative proportion of PO was higher than PC in all of these materials. This indicates that during thermal pyrolysis, the gradual dehydration and condensation of dihydrogen phosphate groups into polyphosphate may have formed PO as the dominant bond in these materials. However, it is also possible that these materials physically adsorbed oxygen, primarily because oxygen can easily be adsorbed in the graphite structure, even at low pressure.

(39) It is to be understood that the present subject matter is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims.