NL2030278B1 - N-go@co-ni12p5-ni3p/ncf composite electrode material and preparation method thereof - Google Patents

N-go@co-ni12p5-ni3p/ncf composite electrode material and preparation method thereof Download PDF

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NL2030278B1
NL2030278B1 NL2030278A NL2030278A NL2030278B1 NL 2030278 B1 NL2030278 B1 NL 2030278B1 NL 2030278 A NL2030278 A NL 2030278A NL 2030278 A NL2030278 A NL 2030278A NL 2030278 B1 NL2030278 B1 NL 2030278B1
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ncf
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Song Caixia
Wang Debao
Xing Miaomiao
Zhou Yanhong
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Qingdao Univ Of Science And Technology
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Abstract

The invention provides a N—GO@Co—NiIJP5—Ni3P/NCF composite electrode material and a preparation method thereof .The preparation method comprises the following steps of, coating transparent liquid formed by mixing methoxymethyl triphenylphosphonium chloride, urea and ethylene glycol on a pretreated nickel—cobalt foam metal sheet, carrying out pyrolysis, carbonization and phosphorization reaction in one step under the protection of aluminum foil wrapping and nitrogen atmosphere to obtain a nitrogen—doped graphene oxide (NGO) — coated Co—doped NiHPS —Ni3P3 composite phosphide nanorod assembly, wherein the assembly grows in situ on a nickel—cobalt foam (NCF) metal sheet current collector, and composite phosphide nanorods are mutually connected and grow to form a sheet—shaped network structure. The composite electrode material has high electrocatalytic hydrogen evolution efficiency in a 1 mol/L’1 KOH solution, has very high catalytic activity and selectivity for electrocatalytic oxidation of HMF to prepare FDCA, and also has very high stability.

Description

N-GORCO-NI;2Ps-NI3P/NCF COMPOSITE ELECTRODE MATERIAL AND PREPARATION
METHOD THEREOF
TECHNICAL FIELD
The invention belongs to the technical field of electrochemi- cal electrode materials, and relates to a N-GORCo-Ni;;Ps—Ni.P/NCF composite electrode material and a preparation method thereof, in particular to a nitrogen-doped graphene oxide (N-GO) coated Co- doped Ni;P5-Ni:P composite electrode material in-situ growing on nickel-cobalt foam (NCE) metal sheet current collector for multi- functional electrolysis and the preparation method thereof.
BACKGROUND ART
H,, as a green energy carrier, is expected to play an im- portant role in the future. Electrocatalytic water decomposition, as a method of providing H;, arouses the interest of the whole world. At present, people have conducted a large amount of re- search on hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) of electrocatalytic water decomposition. In the disclosed technology, phosphide, nitride and sulfide of transition metal such as cobalt and nickel have proven to be excellent HER electrocatalyst, and some transition metal oxides and bimetallic hydroxides exhibit excellent OER performance. In the above- mentioned electrocatalyst, transition metal nickel phosphide is becoming a promising electrocatalyst due to its metal characteris- tics, excellent electrical conductivity and rich valency, and in addition, the surface polarization of phosphorus makes the center of the phosphorus negatively charged, thus accelerating the rapid transmission of electrons and accelerating the redox reaction.
However, it is still not sufficient to replace the noble metal- based catalyst due to its performance, thus requiring a more rea- sonable design to obtain superior performance.
In addition, the OER of the anode is still the difficulty of the complete water decomposition for hydrogen production because a higher over-potential is required to match the rate of HER. At the same time, a product O; of the OER has no significant value, and removal of O:from the mixture of O: with H; is energy-wasting and time-consuming. In this case, the biomass oxidation reaction at- tracts people's attention due to its low over-potential and high commercial value. 5 - Hydroxymethylfurfural (HMF) is considered to be one of the most widely used biomass-derived model molecules and can be further oxidized into a plurality of high value-added com- posite intermediates, such as 2,5 - furandicarboxylic acid (FDCA), etc. In the field of polymer materials, FDCA can replace tereph- thalic acid to produce bic-based polyesters that are biodegradable and have good performance. A conventional heterogeneous catalytic system oxidizing HMF into FDCA typically requires the use of a no- ble metal-based catalyst (such as Au, Pt, Ru, and Pd), which is reacted at high temperatures (30-130 DEG C) and high pressure air or 0; (such as 0.3 -2.0 MPa). The oxidation of HMF to prepare FDCA by electrochemical method can be carried out at ambient tempera- ture, which avoids the use of high-pressure 0; or other dangerous chemical oxidizing agents and is environmentally friendly, but the noble metal-based electrocatalyst is still the most commonly used catalyst. Therefore, the development research of the high- performance non-noble metal electrocatalyst is the key of the in- dustrial application of electrocatalytic reaction. However, the existing high-performance nickel phosphide-based composite elec- trocatalyst has the disadvantages of complex preparation process, low electrocatalytic activity and insufficient cycle stability, and therefore, it is necessary to further explore an efficient, stable and durable nickel-based composite electrode material with simple preparation process and excellent performance. Novel three- component eutectic mixture liquid is elaborately designed as a precursor, the liquid is coated on a pretreated nickel-cobalt foam metal sheet, wrapped by an aluminum foil, and calcined in a simple one-step manner under a nitrogen atmosphere to obtain a N-GO@Co-
Ni;i2Ps-Ni;P/NCF composite electrode material.
SUMMARY
Aiming at the defects that in the prior art, the process of preparing a nickel phosphide-based composite electrode material is complex, multi-step synthesis is required, tight interface cou- pling is difficult to achieve, active sites are low, electrocata- lytic efficiency is low, long-term stability is poor, and the like, the invention discloses a N-GC@Co-Niy,P5-Ni;P/NCF composite electrode material and preparation method thereof, characterized in that a nitrogen-doped graphene oxide {N-GO0) coated Co-doped
Nii2P:-Ni:P composite phosphide nanorod assembly grows in situ on a nickel-cobalt foam (NCF) metal sheet current collector, the compo- site phosphide nanorods grow mutually connected and form a sheet- shaped network structure, and through a liquid precursor coated on a pre-treated nickel-cobalt foam metal sheet and under the protec- tion of aluminum foil wrapping and nitrogen atmosphere, pyrolysis, carbonization and phosphatization reactions complete in one step, and the method specifically comprises the following steps of, (1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the NCF metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultrasonic soaking for 5 min, then placing in 1 mol/L dilute hydrochloric acid for ultra- sonic soaking for 5 min, then taking out NCF and washing for three times with deionized water and absolute ethyl alcohol respective- ly, and drying in a vacuum drying oven at 40 DEG C; (2) mixing 0.001-0.1 mol of methoxymethyl- triphenylphosphonium chloride, 0.001-0.05 mol of urea and 0.001- 0.05 mol of ethylene glycol, and stirring at 30-90 DEG C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the pre-treated NCF in step (1), wrapping with an aluminum foil, heating to 300-650 DEG C under the protection of nitrogen atmos- phere, keeping the temperature for 1-5 h, and cooling to obtain the N-GOQCo-Ni;;P;-Ni;P/NCF composite electrode material.
The invention has the advantages that the designed novel three-component eutectic mixture liquid is used as a precursor, so that precursor carbonization, phosphatization and graphene oxide shell growth and compositing can take place in one step; the gra- phene oxide shell on the surface of the Co-Ni::Ps-Ni3p can effec- tively prevent the catalyst from inactivating, and the Co-Ni;;Ps-
Nis3sP catalyst growing in situ on NCF metal sheet is directly used as an electrode, so that the falling of the catalyst is effective- ly reduced, and the stability is improved; the electrocatalytic activity of the Ni;;P.-Ni:P catalyst can be further improved by mak- ing the electronic structure adjustment of Nii;:Ps-NisP catalyst through Co doping, so that the electrocatalytic activity of the
NiisPs-Ni:P can be further improved; and the synthesized electrocat- alyst is a multifunctional electrocatalyst, can perform electro- catalytic oxidation of 5-hydroxymethylfurfural (HMF), and has high electrocatalytic activity and stability for electrocatalytic de- composition of water for hydrogen production and electrochemical degradation of organic dyes.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows XRD pattern of the N-GORCo-Ni;P;-Ni;P/NCF compo- site electrode material prepared by the method according to Embod- iment 1 of the present invention.
FIG. 2 shows a Raman spectrum (a) and an infrared spectrum (b} of the N-GORCo-Ni::Ps-Ni3P/NCF composite electrode material pre- pared by the method according to Embodiment 1 of the present in- vention.
FIG. 3 shows SEM images with different magnification of the
N-GO@Co-Ni;sP5-NisP/NCF composite electrode material prepared by the method according to Embodiment 1 of the present invention.
FIG. 4 shows TEM (a) and HRTEM (b,c) images of the N-GO@Co-
Nii5Ps-NisP/NCF composite electrode material prepared by the method according to Embodiment 1 of the present invention.
FIG. 5 shows a STEM image and STEM-MAPPING element distribu- tion diagrams of the N-GO@Co-Ni;:P:;-Ni;P/NCF composite electrode material prepared by the method according to Embodiment 1 of the present invention.
FIG. 6 shows the electrocatalytic hydrogen evolution rates of the composite electrode material prepared by the method according to Embodiment 1, Comparative Example 1 and Comparative Example 2 of the present invention.
FIG. 7 shows catalytic performance of the N-GORCo-Ni::Ps-
Ni3P/NCF composite electrode material prepared by the method ac- cording to Embodiment 1 of the present invention for OER and the preparation of FDCA by electrocatalytic oxidation of HMF. (a) LSV curves of water OER and HMF oxidation, (b) selectivity of FDCA from HMF , and (c) cycle stability experiment of FDCA preparation from HMF of. 5
DETAILED DESCRIPTION OF THE EMBODIMENTS
The present invention will be further described in detail be- low with reference to the embodiments.
Embodiment 1: (1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic scaking for 5 min, then taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol respectively, and drying in a vacuum drying oven at 40 DEG C; (2) mixing 0.02 mol of methoxymethyl-triphenylphosphonium chloride, 0.005 mol of urea and 0.01 mol of ethylene glycol, and stirring at 80 DEG C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with an aluminum foil, heating to 450 DEG C under the protection of nitro- gen atmosphere, keeping the temperature for 4 h, and cooling to obtain the N-GORCo-Ni::Ps-NisP/NCF composite electrode material.
Embodiment 2: (1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic soaking for 5 min, then taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol respectively, and drying in a vacuum drying oven at 40 DEG C; (2) mixing 0.02 mol of methoxymethyl-triphenylphosphonium chloride, 0.005 mol of urea and 0.01 mol of ethylene glycol, and stirring at 80 DEG C to form transparent liquid; and
(3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with an aluminum foil, heating to 350 DEG C under the protection of nitro- gen atmosphere, keeping the temperature for 4 h, and cooling to obtain the N-GORCo-Nii:Ps-NisP/NCF composite electrode material.
Embodiment 3: (1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic scaking for 5 min, then taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol respectively, and drying in a vacuum drying oven at 40 DEG C; (2) mixing 0.01 mol of methoxymethyl-triphenylphosphonium chloride, 0.005 mol of urea and 0.02 mol of ethylene glycol, and stirring at 60 DEG C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with an aluminum foil, heating to 450 DEG C under the protection of nitro- gen atmosphere, keeping the temperature for 4 h, and cooling to obtain the N-GO@Co-Ni:sPs-Ni3P/NCF composite electrode material.
Embodiment 4: (1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic soaking for 5 min, then taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol respectively, and drying in a vacuum drying oven at 40 DEG C; (2) mixing 0.02 mol of methoxymethyl-triphenylphosphonium chloride, 0.01 mol of urea and 0.1 mol of ethylene glycol, and stirring at 60 DEG C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with an aluminum foil, heating to 350 DEG C under the protection of nitro-
gen atmosphere, keeping the temperature for 4 h, and cooling to obtain the N-GORCo-Ni;:Ps-Ni:sP/NCF composite electrode material.
Embodiment 5: (1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic soaking for 5 min, then wrapping with the aluminum foil, taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol re- spectively, and drying in a vacuum drying oven at 40 DEG C; (2) mixing 0.03 mol of methoxymethyl-triphenylphosphonium chloride, 0.005 mol of urea and 0.02 mol of ethylene glycol, and stirring at 70 DEG C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with the aluminum foil, heating to 550 DEG C under the protection of nitro- gen atmosphere, keeping the temperature for 2 h, and cocling to obtain the N-GO@Co-Nii2Ps-Ni;P/NCF composite electrode material.
Embodiment 6: (1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic scaking for 5 min, then wrapping with the aluminum foil, taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol re- spectively, and drying in a vacuum drying oven at 40 DEG C; {2) mixing 0.1 mol of methoxymethyl-triphenylphosphonium chloride, 0.05 mol of urea and 0.05 mol of ethylene glycol, and stirring at 80 DEG C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with the aluminum foil, heating to 600 DEG C under the protection of nitro- gen atmosphere, keeping the temperature for 1 h, and cooling to obtain the N-GOE@Co-Ni;;P:-Ni:P/NCF composite electrode material.
Embodiment 7: {1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic soaking for 5 min, then taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol respectively, and drying in a vacuum drying oven at 40 DEG C; {2) mixing 0.02 mol of methoxymethyl-triphenylphosphonium chloride, 0.005 mol of urea and 0.02 mol of ethylene glycol, and stirring at 50 DEG C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with an aluminum foil, heating to 350 DEG C under the protection of nitro- gen atmosphere, keeping the temperature for 4 h, and cooling to obtain the N-GOE@Co-Ni;.P5-Ni;P/NCF composite electrode material.
Comparative Example 1: (1) Pretreatment of the nickel foam (NF) metal sheet, specif- ically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic soaking for 5 min, then taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol respectively, and drying in a vacuum drying oven at 40 DEG C; (2) mixing 0.02 mol of methoxymethyl-triphenylphosphonium chloride, 0.005 mol of urea and 0.01 mol of ethylene glycol, and stirring at 80 DEG C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with an aluminum foil, heating to 450 DEG C under the protection of nitro- gen atmosphere, keeping the temperature for 4 h, and cooling to obtain the N-GO@Co-Ni:;Ps-Nis3P/NCF composite electrode material.
Comparative Example 2: (1) Pretreatment of the nickel-cobalt foam metal sheet, spe- cifically, cutting the nickel-cobalt foam metal sheet into square pieces with the size of 1 cm x 1 cm, placing in acetone for ultra- sonic soaking for 5 min, then placing in 1 mol/L dilute hydrochlo- ric acid for ultrasonic soaking for 5 min, then taking out foamed nickel cobalt and washing for three times with deionized water and absolute ethyl alcohol respectively, and drying in a vacuum drying oven at 40 DEG C; (2) mixing 0.02 mol of methoxymethyl-triphenylphosphonium chloride, 0.005 mol of urea and 0.01 mel of ethylene glycol, and stirring at 80 DEG C to form transparent liquid; and {3) coating the transparent liquid obtained in step (2) on the nickel-cobalt foam pre-treated in step (1), wrapping with an aluminum foil, heating to 450 DEG C under the protection of nitro- gen atmosphere, keeping the temperature for 4 h, and cooling to obtain the N-GO@Co-Ni:;Ps-Niz3P/NCF composite electrode material.
FIG. 1 shows XRD pattern of the N-GO@Co-Ni;:Ps-Ni:P/NCF compo- site electrode material prepared by the method according to Embod- iment 1 of the present invention. As can be seen from Figure 1, in addition to diffraction peaks of metallic nickel, all diffraction peaks correspond to diffraction peaks of Ni:P (JPDS 74 -1384) and
Nii2Ps (JPDS 74 -1381), respectively. This confirms that the pre- pared product is a phosphide composite material.
FIG. 2 shows a Raman spectrum (a) and an infrared spectrum {b) of the N-GOQ@Co-Ni:;Ps-NisP/NCF composite electrode material pre- pared by the method according to Embodiment 1 of the present in- vention. As can be seen from the Raman spectrum, there are two typical characteristic peaks at 1346 cmt and 1585 cmt, respective- ly matching D peak and G peak of graphite structure carbon, and the intensity ratio I;/Is« of the D peak and the G peak is equal to 0.84, indicating that the obtained product has incomplete graphi- tization degree and more defects. The absorption peak of 3400 cm™ in the infrared spectrum corresponds to the -OH stretching vibra- tion on the carbon, the absorption at 2920 cm™ and 2850 cmt corre- sponds to the alkyl stretching vibration of CH or CH, and the peak at 1630 cm} is the skeletal vibration peak at C = C or C-C , indi- cating the presence of a graphene structure on a sample, and the peak at 1717 cmt and 1130 cm? from vibration at C=0 and C-0. The infrared spectrum further indicates that the carbon of a graphene structure in the sample contains a large amount of -OH, C =0 and
C-0, and the carbon is the carbon of a graphene oxide structure.
FIG. 3 shows SEM images with different magnification of the
N-GO@RCo-Nii;;Ps-Ni:P/NCF composite electrode material prepared by the method according to Embodiment 1 of the present invention. As can be seen from FIG. 3a, a three-dimensional porous channel open skeleton structure of the nickel-cobalt foam metal sheet can be observed, and the surface of a skeleton is coated with a layer of material. As can be seen from FIG. 3b, a layer of array or assem- bly structure similar to nanosheets grows in situ on the surface of the nickel-cobalt foam skeleton, and after further magnifica- tion, it can be seen from FIG. 3c that the nanosheets are actually sheet-shaped network structures formed by mutual connection and growth among nanorods, the network structure of a composite phos- phidized nickel sheet and the porous channel open skeleton struc- ture of the nickel-cobalt foam metal sheet can enable the catalyst to expose more active sites, provide a rapid conductive channel, accelerate the electron/charge transfer rate, and greatly improve the electrocatalytic activity and stability.
FIG. 4 shows TEM (a) and HRTEM (b, c¢) images of the N-GO@Co-
Nii2Ps-Ni:P/NCF composite electrode material prepared by the method according to Embodiment 1 of the present invention. As can be seen from FIG. 4a, the nanorods growing in situ on the skeleton of the nickel-cobalt foam are overlapped with each other to form the sheet-shaped network structure, and the diameter of the single na- norod is about 25 nm. FIG. 4b is a HRTEM image of the single na- norod. It can be seen from figure that the nanorod is coated with a GO carbon layer, and the nanorod crystal lattice is obvious. It can be clearly observed from figure 4c of magnified area that the nanorod phosphide exhibits various lattice stripes, and Moire fringe can be clearly observed, indicating that the nanorods are formed by superposition of a plurality of layers of nanosheets.
The interplanar crystal spacing of the edges of the nanorods is 0.200 nm and 0.224 nm, corresponding to (240) and (400) crystal planes of Ni3P, and the interplanar crystal spacing inside the na- norods is 0.274 nm, corresponding to a (130) crystal plane of
NiisPs, further illustrating that the composite electrode is com-
posed of the GO-coated Ni;:p;-Ni3P composite material.
FIG. 5 shows a STEM image and STEM-Mapping element distribu- tion diagrams of the N-GO@Co-Ni:2Ps-NisP/NCF composite electrode material prepared by the method according to Embodiment 1 of the present invention. The STEM image shows the sheet-shaped network structure formed by overlapping the nanorods more clearly, and the element distribution of Ni and P elements is the most compact, in- dicating that the nanorods are mainly composite nickel phosphide, which is also consistent with the XRD results. Co elements are uniformly distributed. In combination with the XRD results, the CO exists in the lattice of the composite nickel phosphide, and there is no phosphide crystal phase of independent CO. The carbon ele- ment distribution is also obvious, but the displayed nanorods are thicker, indicating that C is coated on the surface of the compo- site nickel phosphide nanorod, which is also consistent with the
HRTEM results. Similarly, the distribution of O and N elements are relatively poor, and the displayed nanorods are also thicker, in- dicating that O and N elements mainly exist in the carbon layers on the surface of the nanorods, and further indicating that the graphene oxide is N-doped, and an electrode material is a N-GOGCo-
Nii2Ps5-Ni:P composite material.
FIG. 6 shows the electrocatalytic hydrogen evolution rates of the composite electrode material prepared by the method according to Embodiment 1, Comparative Example 1 and Comparative Example 2 of the present invention. As can be seen from figure, the over- potential of the composite electrode material According to embodi- ment 1 is 53.8 mV at 10 mA cm‘ current, far lower than the over- potential of 212 mV and 235 mV at 10 mA cm° current of the compo- site electrode material according to Comparative Example 1 and
Comparative Example 2, indicating that the HER activity of the N-
GORCo-Ni;sPs-NisP/NCF composite electrode material prepared by the method according to Embodiment 1 of the present invention is much higher than that of the composite electrode material according to
Comparative Example 1 and Comparative Example 2, and the doping of the Co element in the composite phosphide and the coating of N-GO on the composite phosphide can greatly improve the electrocatalyt- ic activity of the composite phosphide.
FIG. 7 shows catalytic performance of the N-GORCo-Ni;:Ps-
Ni3P/NCF composite electrode material prepared by the method ac- cording to Embodiment 1 of the present invention for OER and the preparation of FDCA by electrocatalytic oxidation of HMF. (a) LSV curves of water OER and HMF oxidation, (b) selectivity of FDCA from HMF, and (c) cycle stability experiment of FDCA preparation from HMF . FIG. 7a is the LSV curve of OER and FDCA preparation by electrocatalytic oxidation of HMF by using the composite electrode material according to Embodiment 1 . It can be seen that 1.57 V of over-potential is required for OER reaction of 1 mol L KOH aque- ous solution to achieve 20 mA/cm® current requires. However, for electrocatalytic oxidation of HMF to prepare FDCA, the over- potential at 20 mA/cm® is reduced to 1.37 V, indicating that under alkaline conditions, the performance of electrocatalytic oxidation of HMF to prepare FDCA is better than OER by using the composite electrode material according to Embodiment 1. FIG. 7b shows that the concentration of HMF and various oxidation products in a high performance liquid chromatography analysis system changes over time during the preparation of FDCA by electrocatalytic oxidation of HMF, and as the concentration of HMF decreases, the yield of
FDCA gradually increases, the concentration of FDCA after 120 min reaches the maximum, close to 100%, while the concentration of other oxidation products is small and does not significantly change, indicating that the composite electrode material according to Embodiment 1 has high selectivity when used for electrocatalyt- ic oxidation of HMF to prepare FDCA. FIG. 7c shows that the compo- site electrode material is recycled for six times for electrocata- lytic oxidation of HMF to prepare FDCA, and the yield of FDCA is not significantly reduced, indicating that the composite electrode material has very high catalytic activity and selectivity for electrocatalytic oxidation of HMF to prepare FDCA, and also has very high stability.
Further, the N-GO@Co-Ni;:P5s-Ni3P/NCF composite electrode mate- rial prepared by the method according to Embodiment 1 of the pre- sent invention is used for electrocatalytic degradation of common organic dyes in the aqueous solution, and the result shows that the composite electrode material prepared by the method has good electrocatalytic activity for electrocatalytic degradation of com- mon organic dyes, and can be used for electrocatalytic oxidation treatment of organic wastewater.
The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present inven- tion are not limited by the above-mentioned embodiments, and any other changes, substitutions, simplification and the like made without departing from the principle and the process of the pre- sent invention are all equivalent permutations, and all shall be included in the protection scope of the present invention.

Claims (1)

CONCLUSIESCONCLUSIONS 1. Werkwijze voor het bereiden van een N-GORCo-Ni4;Ps-NisP/NCF com- posiet elektrodemateriaal, met het kenmerk, dat een met stikstof gedoteerd grafeenoxide (N-GO) bekleed met Co gedoteerde Ni;:P5s-Ni3P samengestelde fosfide nanostaaf assemblage in situ groeit op een stroomcollector van een nikkel-kobaltschuim NCF metalen plaat, waarbij samengestelde fosfide nanostaafjes onderling zijn verbon- den en groeien tot een plaatvormige netwerkstructuur, en waarbij door een vloeibare precursor die is aangebracht op een voorbehan- delde nikkel-kobaltschuim metalen plaat en onder de bescherming van aluminium folieverpakking en stikstofatmosfeer, pyrolyse, car- bonisatie en fosfateringsreacties in één stap worden voltooid en waarbij de werkwijze specifiek de volgende stappen omvat van: (1) voorbehandeling van de metaalplaat van nikkel-kobaltschuim, met name het snijden van de metaalplaat van nikkel-kobaltschuim in vierkante stukken van 1 cm x 1 cm, in aceton plaatsen voor ultra- soon weken gedurende 5 minuten en vervolgens in 1 mol/L verdund zoutzuur plaatsen voor ultrasoon weken gedurende 5 minuten, ver- volgens geschuimd nikkelkobalt eruit halen en driemaal wassen met respectievelijk gedeïoniseerd water en absolute ethylalcohol, en drogen in een vacuümdroogoven bij 40 °C; (2) menging van 0,001 - 0,1 mol methoxymethyl-trifenylfosfonium- chloride, 0,001 - 0,05 mol ureum en 0,001 - 0,05 mol ethyleengly- col en roeren bij 30 - 90 °C om transparante vloeistof te vormen; en (3) bekleding van de in stap (2) verkregen transparante vloeistof op het in stap (1) voorbehandelde nikkel-kobaltschuim, omwikkelen met aluminiumfolie, verwarmen tot 300 - 650 °C onder bescherming van een stikstofatmosfeer, waarbij de temperatuur gedurende 1 - 5 uur in stand wordt gehouden en koeling om het N-GO@Co-Ni;:Ps- NisP/NCF composiet elektrodemateriaal te verkrijgen.A method for preparing an N-GORCo-Ni4;Ps-NisP/NCF composite electrode material, characterized in that a nitrogen-doped graphene oxide (N-GO) coated with Co-doped Ni::P5s-Ni3P composite phosphide nanorod assembly in situ grows on a current collector of a nickel-cobalt foam NCF metal plate, where composite phosphide nanorods are interconnected and grow into a plate-like network structure, and where a liquid precursor applied to a pre-treated nickel cobalt foam metal sheet and under the protection of aluminum foil packaging and nitrogen atmosphere, pyrolysis, carbonization and phosphating reactions are completed in one step, and the process specifically includes the following steps of: (1) pretreatment of the metal sheet of nickel cobalt foam, namely cutting the nickel-cobalt foam metal sheet into 1 cm x 1 cm square pieces, placing in acetone for ultrasonic soaking for 5 minutes, and then placing in 1 mol/L diluted hydrochloric acid for ultrasonic soaking for 5 minutes, then take out foamed nickel cobalt and wash three times with deionized water and absolute ethyl alcohol, respectively, and dry in a vacuum drying oven at 40 °C; (2) mixing 0.001-0.1 mol of methoxymethyl-triphenylphosphonium chloride, 0.001-0.05 mol of urea and 0.001-0.05 mol of ethylene glycol and stirring at 30-90°C to form transparent liquid; and (3) coating the transparent liquid obtained in step (2) on the pre-treated nickel-cobalt foam in step (1), wrapping with aluminum foil, heating to 300-650°C under the protection of a nitrogen atmosphere, keeping the temperature for 1 - 5 hours and cooling to obtain the N-GO@Co-Ni 2 :Ps-NisP/NCF composite electrode material.
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