CN114622242B - Ni/NiO nano heterojunction porous graphite carbon composite material and preparation method and application thereof - Google Patents
Ni/NiO nano heterojunction porous graphite carbon composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a Ni/NiO nano heterojunction porous graphite carbon composite material, which comprises the following steps: providing a Ni-MOFs precursor material; and calcining the Ni-MOFs precursor material in a reducing atmosphere, and cooling to obtain the Ni-NiO nano heterojunction porous graphite carbon composite material. The invention also discloses the Ni/NiO nano heterojunction porous graphite carbon composite material prepared by the method and application of the composite material as an electrocatalyst for catalyzing hydrogen evolution reaction under alkaline conditions. According to the invention, the target product Ni/NiO-PGC can be obtained through solvothermal reaction and a one-step reduction pyrolysis method, the operation is simple, and the product is uniform.
Description
Technical Field
The invention relates to the technical field of nano material preparation and electrochemistry, in particular to a Ni/NiO nano heterojunction porous graphite carbon composite material and a preparation method and application thereof.
Background
With the development of society and the rapid growth of population, the problems of environmental pollution and energy shortage are receiving wide attention. Therefore, it is urgent to develop clean and sustainable energy and to explore energy storage and conversion technologies. And hydrogen energy is regarded as the most ideal energy source in the future as a new zero-pollution and high-energy-density energy source. According to the statistics of international renewable energy agency (IRENA), there are three main ways for industrially producing hydrogen at present: steam methane reforming, coal gasification and water electrolysis, the former two of which produce over 95% of the total Hydrogen, while the amount of Hydrogen produced by electrolysis of water is only around 4% (see IRENA-Hydrogen from Renewable Power 2018). But the method is considered to be the most effective hydrogen production method due to the characteristics of environmental protection, economy and the like of hydrogen production by electrocatalytic water splitting and the capability of storing electric energy generated by renewable energy sources (such as solar energy, tidal energy and the like) into chemical energy. The electrolytic decomposition of water involves two half-reactions: hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) undergo multiple electron transfer processes, so their kinetics are slow. To date, platinum (Pt), ruthenium (Ru) and iridium (Ir) are still considered as the most active materials for electrocatalytic water splitting, but their low earth abundance and high price limit their large-scale industrial application. Therefore, the development of the high-efficiency and stable non-noble metal electrocatalyst is the key of the industrial application of the hydrogen production by water electrolysis.
In the research of non-noble metal catalysts, since the transition metal Ni has better H adsorption activity, it is considered as the most promising metal material to replace Pt-based catalysts. And the rate of water dissociation is slow in an alkaline medium, so that the electrocatalytic activity is greatly reduced. Transition metal oxides are reported in the literature to be effective in promoting water decomposition (see l.zhao, y.zhang, z.zhao, q.h.zhang, l.b.huang, l.gu, g.lu, j.s.hu and l.j.wan, natl.sci.rev.,2020,7, 27-36.), so constructing a transition metal/transition metal oxide heterojunction is an effective strategy for increasing the overall rate of electrocatalytic hydrogen evolution reaction. But Ni/NiO is less conductive and tends to aggregate, making it less electrochemically desirable. Complexing them with conductive carbon nanostructures to obtain more catalytically active sites and enhanced conductivity is an ideal way to increase their catalytic HER activity. As reported by Jaephil Cho et al, ni-NiO nitrogen-doped reduced graphene oxide (Ni-NiO/N-rGO) shows excellent OER, HER and ORR multifunctional catalytic activity in an alkaline medium. However, this strategy requires the introduction of electrically conductive carbon nanostructured graphene in advance, and requires multi-step redox calcination, the preparation process is complicated and energy-consuming, and the distribution of the generated Ni-NiO on the nitrogen-doped reduced graphene oxide is not uniform (see x.liu, w.liu, m.ko, m.park, m.g.kim, p.oh, s.chae, s.park, a.casimir, g.wu and j.cho, adv.funct.mater. 2015,25, 5799-5808.). Dai et al reported that nano NiO/Ni heterojunctions (NiO/Ni-CNTs) prepared on the side walls of carbon nanotubes are an efficient HER electrocatalyst, but the preparation method requires calcination at low pressure of 1.5torr (about 200 Pa), and also pre-oxidation of carbon nanotubes, and the preparation process is complicated (see m.gong, w.zhou, m.c.tsai, j.zhou, m.guan, m.c.lin, b.zhang, y.hu, d.y.wang, j.yang, s.j.pennyook, b.j.wang and h.dai, nat.commu., 2014,5, 4695-4701.). Therefore, exploring how to construct rich Ni/NiO heterojunction interfaces, reduce the aggregation of the interfaces and realize the good combination of the Ni/NiO heterojunction and the carbon nano structure is still the key problem to be solved for improving the electrochemical performance of the electrocatalyst. It remains challenging to develop a simple and controllable method to prepare non-noble metal electrocatalysts with metal/metal oxide heterojunction interfaces with efficient HER activity.
Disclosure of Invention
The invention aims to solve the technical problem of providing a synthesis method of a Ni/NiO heterojunction porous graphite carbon composite material derived from MOFs (metal-organic frameworks) in-situ reduction pyrolysis, and the synthesis method is named as Ni/NiO-PGC, wherein Ni represents a nickel simple substance, niO represents nickel oxide, and PGC represents porous graphitized carbon (porous graphite carbon). The target product Ni/NiO-PGC can be obtained through solvothermal reaction and a one-step reduction pyrolysis method, the operation is simple, and the product is uniform.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a Ni/NiO nano heterojunction porous graphite carbon composite material, which comprises the following steps:
providing a Ni-MOFs precursor material;
and calcining the Ni-MOFs precursor material in a reducing atmosphere, and cooling to obtain the Ni/NiO nano heterojunction porous graphite carbon composite material.
Further, the preparation method of the Ni-MOFs precursor material comprises the following steps:
dissolving nickel salt and organic ligand in a mixed solvent of an organic solvent and water, and reacting for 3-12 hours at 120-180 ℃ to obtain the stacked-layer Ni-MOFs precursor material.
In the present invention, the nickel salt is preferably nickel nitrate hexahydrate, the organic ligand is preferably terephthalic acid, and the organic solvent is preferably N, N-dimethylformamide.
In the present invention, the molar ratio of the nickel salt to the organic ligand is 2. Preferably, the molar ratio of nickel salt to ligand is 1.
In the present invention, the reaction temperature is preferably 150 ℃ and the reaction time is preferably 4 hours.
In the invention, after the reaction is finished, the method also comprises the steps of washing and drying the reaction product. Preferably washing the reaction product by using deionized water and ethanol, and drying by using an air-blast drying oven; wherein, the drying temperature is preferably 40-60 ℃, and the drying time is 2-12 h; more preferably, the drying temperature is 60 ℃ and the drying time is 12h.
In the present invention, the reducing atmosphere used is preferably H 2 /N 2 Atmosphere with H 2 The atmosphere causes a great risk to the reaction, so the invention uses H 2 /N 2 The mixed gas is used as reducing atmosphere. Wherein, in order to ensure the safety, H in the mixed gas 2 The content of (B) is not preferably too high, and is preferably less than 10%. Preferably, the reducing atmosphere is 5to 10 percent of H 2 /N 2 The "5%" and "10%" as used herein mean H in the gas mixture 2 Volume fraction of (a). More preferably, the reducing atmosphere is 10% H 2 /N 2 In the atmosphere, a proper amount of NiO is reduced into Ni, and the obtained Ni/NiO nano heterojunction material has better catalytic performance.
In the invention, the calcination temperature is 400-600 ℃, and the calcination time is 30min-12 h; preferably, the calcination temperature is 400 ℃ and the calcination time is 1h. The rate of temperature rise before calcination is preferably 3 to 10 ℃/min.
After calcination, the product is cooled to room temperature, wherein the cooling process is carried out in a reducing atmosphere.
The invention also provides the Ni/NiO nano heterojunction porous graphite carbon composite material prepared by the method, and the composite material has good electrocatalytic performance.
The invention further provides application of the Ni/NiO nano heterojunction porous graphite carbon composite material as an electrocatalyst, in particular application of catalyzing hydrogen evolution reaction under alkaline conditions.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation process is simple, the target product Ni-NiO nano heterojunction porous graphite carbon can be obtained through solvothermal reaction and one-step reduction pyrolysis method, the carbon nano structure does not need to be pretreated, and the operation is simple.
2. The invention adopts the synthesis method of 'in-situ reduction pyrolysis', and the obtained product has uniform appearance.
3. In the preparation process, the reduced Ni nano-particles can catalyze the graphitization of the surrounding carbon, so that the Ni/NiO heterojunction is uniformly embedded on the porous graphite carbon, and the combination of the Ni/NiO heterojunction and the carbon matrix is good.
4. The Ni/NiO-PGC nano material prepared by the invention catalyzes HER reaction in alkaline electrolyte (pH = 14), shows excellent catalytic performance and has the capacity of catalyzing HER reaction at 10mA · cm -2 At a current density of (3), the value of HER overpotential is only 31.6mV, and the Tafel slope is also as low as 73.51mV dec -1 . And at 10 mA-cm -2 The current density of the alloy is not obviously reduced after being operated for at least 65 hours, and the long-term stability is shown.
Drawings
FIG. 1 is an X-ray powder diffraction (PXRD) pattern of Ni-MOFs;
FIG. 2 is a Scanning Electron Microscope (SEM) image and a Transmission Electron Microscope (TEM) image of Ni-MOFs;
FIG. 3 is an X-ray powder diffraction (PXRD) pattern of Ni/NiO-PGC;
FIG. 4 is a Scanning Electron Microscope (SEM) image (a), a Transmission Electron Microscope (TEM) image (b), a High Resolution Transmission Electron Microscope (HRTEM) image (c, d), a Selected Area Electron Diffraction (SAED) image (e), and an energy distribution surface scanning (EDX-Mapping) image (f) of Ni/NiO-PGC;
FIG. 5 is a Raman spectrum of Ni/NiO-PGC;
FIG. 6 is an energy dispersive X-ray spectroscopy (EDX) plot of Ni/NiO-PGC;
FIG. 7 is an X-ray photoelectron spectroscopy (XPS) chart of Ni/NiO-PGC;
FIG. 8 is a Ni/NiO-PGC-5% energy dispersive X-ray spectroscopy (EDX) diagram;
FIG. 9 is an X-ray photoelectron spectroscopy (XPS) plot of Ni/NiO-PGC-5%;
FIG. 10 is an X-ray powder diffraction (PXRD) pattern of NiO-PC;
FIG. 11 is an X-ray photoelectron spectroscopy (XPS) graph of NiO-PC;
FIG. 12 is a Transmission Electron Microscope (TEM) image of NiO-PC;
FIG. 13 is a graph of HER polarization in 1.0M KOH for NiO-PC;
FIG. 14 is a graph of HER polarization in 1.0M KOH for Ni/NiO-PGC (a), tafel slope plot (b), nyquist plot (c), double layer capacitance plot (d), current density of 10mA cm -2 Comparative histogram (e) and chronopotentiometric (f) of overpotential and current density at 150 mV.
Detailed Description
The present invention is further described below in conjunction with the drawings and the embodiments so that those skilled in the art can better understand the present invention and can carry out the present invention, but the embodiments are not to be construed as limiting the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
Example 1: preparation of Ni/NiO-PGC
Respectively weighing 29.01 (0.10 mmol) of nickel nitrate hexahydrate and 33.20mg (0.20 mmol) of terephthalic acid, respectively dissolving the nickel nitrate hexahydrate and the terephthalic acid in 4.5mL of N, N-Dimethylformamide (DMF), transferring the obtained solution to a stainless steel reaction kettle containing a polytetrafluoroethylene lining after dissolving, adding 3mL of deionized water, stirring to form a uniform solution, sealing, placing the uniform solution in a drying oven, reacting for 4 hours at 150 ℃, naturally cooling to room temperature after the reaction is finished, washing with the deionized water and ethanol, and drying for 12 hours at 60 ℃ in a blast drying oven to obtain the Ni-MOFs precursor. 60mg of Ni-MOFs were placed in a 2cm by 5cm porcelain boat and placed in a tube furnace at 10% H 2 /N 2 After the air flow is aerated for 30 minutes to wash out residual air in the tube furnace, the temperature is raised to 400 ℃ at the speed of 10 ℃/min and kept for 1 hour. And after the calcination is finished and the temperature is cooled to room temperature, obtaining a Ni/NiO-PGC sample, wherein Ni represents a nickel simple substance, niO represents nickel oxide, and PGC represents porous graphitized carbon (porous graphitized carbon).
FIG. 1 is an X-ray powder diffraction pattern of Ni-MOFs, and it can be seen from FIG. 1 that the powder diffraction Pattern (PXRD) of Ni-MOFs is matched with the peak of the simulated spectrum (CCDC No. 638866).
As shown in FIG. 2, the SEM image shows that Ni-MOFs is an assembly formed by stacking multiple nano sheets.
As shown in FIG. 3, the powder diffraction Pattern (PXRD) of Ni/NiO-PGC was consistent with Ni Standard card (PDF # 96-210-2279) and NiO Standard card (PDF # 01-073-1523).
As shown in FIG. 4, SEM (4 a) and TEM (4 b) shows that Ni/NiO-PGC also retained the overall morphology of Ni-MOFs, and uniform Ni/NiO nanoparticles and porous morphology by pyrolysis can be seen. As shown in FIG. 4c, the terephthalic acid ligand pyrolyzes around the Ni/NiO particles to form graphitized carbon. The high resolution transmission electron micrograph (4 d) shows 0.204nm and 0.178nm corresponding to the 111 and 002 planes of Ni and 0.241nm and 0.209nm corresponding to the 111 and 200 planes of NiO, respectively, indicating the formation of a Ni/NiO heterojunction. As shown in FIG. 4e, the Selected Area Electron Diffraction (SAED) pattern of Ni/NiO-PGC showed good crystallinity of Ni/NiO and the diffraction pattern was consistent with high resolution transmission electron microscopy and PXRD results. As shown in FIG. 4f, the Ni, O and C in the Ni/NiO-PGC are distributed uniformly.
As shown in FIG. 5, the absorption peak of NiO in Ni/NiO-PGC is shown in the Raman spectrum at 1327cm -1 And 1591cm -1 The absorption peaks at (A) are the D peak and the G peak of the graphitized carbon.
As shown in FIG. 6, the ratio of Ni to O was 2.63, which was greater than 1, demonstrating that some NiO was reduced to Ni.
As shown in FIG. 7, ni/NiO-PGC photoelectron spectroscopy (XPS) showed that Ni is a mixed valence of 0 and +2, and the peak at 852.3eV is assigned to Ni 0 2p of 3/2 While the peaks of 853.6eV and 855.7eV are ascribed to Ni 2+ 2p 3/2 Multiple split peaks of (a). The coexistence of the Ni simple substance and NiO and the existence of the Ni/NiO heterojunction interface are proved.
Example 2: preparation of Ni/NiO-PGC-5%
60mg of Ni-MOFs were placed in a porcelain boat of 2cm by 5cm and placed in a tube furnace at 5% H 2 /N 2 After the air flow is aerated for 30 minutes to wash out residual air in the tube furnace, the temperature is raised to 400 ℃ at the speed of 10 ℃/min and kept for 2 hours. And cooling to room temperature after the calcination is finished to obtain a Ni/NiO-PGC-5% sample.
As shown in FIG. 8, the ratio of Ni to O in Ni/NiO-PGC-5% was equal to 1.36, which was lower than that in Ni/NiO-PGC, indicating that H was 5% 2 N 2 Less NiO is reduced to Ni simple substance under the atmosphere. XPS also shows Ni 0 The peak area ratio of the binding energy of (1) was smaller than that of Ni/NiO-PGC (FIG. 9), which is consistent with the EDX results.
Comparative example 1: preparation of NiO-PC
60mg of Ni-MOFs are placed in a porcelain boat of 2cm multiplied by 5cm and placed in a tube furnace, and high-purity N is generated in non-reducing gas 2 After the air flow is aerated for 30 minutes to wash out residual air in the tube furnace, the temperature is raised to 400 ℃ at the speed of 10 ℃/min and kept for 8 hours. And cooling to room temperature after the calcination is finished to obtain the NiO-PC sample. Wherein NiO is nickel oxide, and PC represents porous carbon (porus carbon).
As shown in FIG. 10, only NiO characteristic peak appeared in PXRD result of NiO-PC sample, and XPS analysis result also showed that only Ni attributed to NiO existed 2+ Peak of (d) (fig. 11).
The transmission electron microscope image in FIG. 12 shows that the morphology of NiO-PC is similar to that of Ni/NiO-PGC, the overall morphology of Ni-MOFs is maintained, niO particles are formed and embedded in porous carbon, and a higher-resolution TEM image shows that graphitized carbon does not exist in NiO-PC. NiO-PC showed poor HER performance (FIG. 13).
Example 3: HER performance test in alkaline electrolyte
The whole electrocatalysis test is carried out under a standard three-electrode system, 5mg of Ni/NiO-PGC sample is dispersed in 485 mu l of isopropanol, 15 mu l of 0.5wt.% perfluorosulfonic acid type polymer (nafion) solution is added, 50 mu l of the solution is dripped on 0.5cm multiplied by 1cm of carbon paper after ultrasonic homogenization, the carbon paper is used as a working electrode after drying, the reference electrode is an Ag/AgCl (saturated chlorine KCl solution) electrode, and the auxiliary electrode is a platinum wire electrode. The electrolyte solution used for the Linear Sweep Voltammetry (LSV) test was a 1M KOH solution, the potential was swept over a range of-0.8-0V vs RHE, the sweep rate was 5mV/s, and the data were all compensated by iR.
As shown in FIGS. 14 (a), (b) and (c), ni/NiO-PGC showed excellent HER electrocatalytic properties at 10 mA-cm -2 The overpotential value is only 31.6mV and the Tafel slope is also as low as 73.51mV dec -1 And has smaller electrochemical impedance and larger Cdl value, reflecting that Ni/NiO-PGC has larger electrochemical active area (FIG. 14 d). As shown in FIG. 14e, ni/NiO-PGC, ni/NiO-PGC-5% and Pt/C at a current density of 10mA cm -2 The overpotentials of (A) are 31.6mV,51.6mV and 17.6mV, respectively, and the current densities at an overpotential of 150mV are 147.7mA · cm, respectively -2 ，67.26mA·cm -2 And 189.58mA · cm -2 Ni/NiO-PGC showed HER performance similar to that of 20% commercial Pt/C.
Example 4: OER stability Performance test
The chronopotentiometric test was carried out under a standard three-electrode system (reference example 3) by inserting the reference electrode, the auxiliary electrode and the working electrode into a saturated 1.0M KOH solution, and the current density tested was constant at 10 mA-cm -2 。
As shown in FIG. 14f, the electrocatalytic performance of Ni/NiO-PGC was not significantly decreased after 65 hours at constant current potentiometric test, showing excellent long-term stability.
In conclusion, the target product Ni-NiO nano heterojunction porous graphite carbon can be obtained through the solvothermal reaction and the one-step reduction pyrolysis method, the process is very simple, and compared with the preparation method of the Ni/NiO heterojunction material in the prior art, the method has the advantages that the carbon nano structure is not required to be pretreated, the generated Ni/NiO heterojunction is uniformly distributed on the porous graphite carbon, and the Ni/NiO heterojunction is well combined with the carbon matrix. The Ni/NiO-PGC nano material catalyzes HER reaction in alkaline electrolyte, shows excellent catalytic performance and has good long-term stability.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitutions or changes made by the person skilled in the art on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (8)
1. A preparation method of a Ni/NiO nano heterojunction porous graphite carbon composite material is characterized by comprising the following steps:
providing a Ni-MOFs precursor material;
calcining the Ni-MOFs precursor material in a reducing atmosphere, and cooling to obtain the Ni/NiO nano heterojunction porous graphite carbon composite material;
the preparation method of the Ni-MOFs precursor material comprises the following steps: dissolving nickel salt and organic ligand in a mixed solvent of an organic solvent and water, and reacting for 3-12 hours at 120-180 ℃ to obtain the Ni-MOFs precursor material; the nickel salt is nickel nitrate hexahydrate, the organic ligand is terephthalic acid, and the organic solvent is N, N-dimethylformamide.
2. The preparation method of the Ni/NiO nano-heterojunction porous graphitic carbon composite material according to claim 1, wherein the molar ratio of the nickel salt to the organic ligand is 2.
3. The preparation method of the Ni/NiO nano-heterojunction porous graphitic carbon composite material according to claim 1, wherein after the reaction is finished, the reaction product is washed by water and ethanol and dried at 40-60 ℃ for 2-12 h.
4. The method for preparing the Ni/NiO nano-heterojunction porous graphitic carbon composite material according to claim 1, wherein the reducing atmosphere used is H 2 /N 2 。
5. The method for preparing the Ni/NiO nano-heterojunction porous graphite carbon composite material according to claim 4, wherein the reducing atmosphere is 5-10% of H 2 /N 2 An atmosphere.
6. The preparation method of the Ni/NiO nano-heterojunction porous graphitic carbon composite material according to claim 1, wherein the calcination temperature is 400-600 ℃ and the calcination time is 30min-12h.
7. The Ni/NiO nano-heterojunction porous graphitic carbon composite prepared according to the method of any one of claims 1-6.
8. The use of the Ni/NiO nano-heterojunction porous graphitic carbon composite of claim 7 as an electrocatalyst for catalyzing hydrogen evolution reactions under alkaline conditions.
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