CN113731459A - Nitrogen-doped hydrogen terminal diamond and preparation method thereof - Google Patents
Nitrogen-doped hydrogen terminal diamond and preparation method thereof Download PDFInfo
- Publication number
- CN113731459A CN113731459A CN202110821200.3A CN202110821200A CN113731459A CN 113731459 A CN113731459 A CN 113731459A CN 202110821200 A CN202110821200 A CN 202110821200A CN 113731459 A CN113731459 A CN 113731459A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- hydrogen
- doped
- terminated
- diamond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 130
- 239000010432 diamond Substances 0.000 title claims abstract description 130
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 103
- 238000000034 method Methods 0.000 claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 230000006911 nucleation Effects 0.000 claims abstract description 23
- 238000010899 nucleation Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- 230000007547 defect Effects 0.000 claims abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000002113 nanodiamond Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 27
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000012417 linear regression Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000009620 Haber process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Electromagnetism (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the field of photocatalysis, and discloses a nitrogen-doped hydrogen terminal diamond and a preparation method thereof, wherein the preparation method comprises the following steps: performing nucleation on the pretreated substrate; and then growing a nitrogen-doped polycrystalline diamond layer on the nucleated substrate by a microwave plasma chemical vapor deposition method, and carrying out hydrogenation treatment on the nitrogen-doped polycrystalline diamond layer to obtain the nitrogen-doped hydrogen-terminated diamond. The nitrogen-doped hydrogen-terminated diamond comprises hydrogen-terminated polycrystalline diamond, wherein the hydrogen-terminated polycrystalline diamond is doped with nitrogen atoms, and the doping concentration of the nitrogen atoms is more than or equal to 1017cm‑3And the doped nitrogen atoms form nitrogen vacancy color center defects in the hydrogen-terminated polycrystalline diamond; of hydrogen-terminated polycrystalline diamondThe two-dimensional cavity air density is more than or equal to 1010cm‑2. The nitrogen vacancy defect is utilized to realize catalytic reduction of nitrogen under the illumination condition, the polycrystalline diamond is adopted to be a cheaper material, the cost is greatly reduced, no renewable resources are consumed and discharged in the catalysis process, and the method is green and environment-friendly and promotes sustainable development.
Description
Technical Field
The invention belongs to the field of photocatalysis, and relates to a nitrogen-doped hydrogen-terminated diamond and a preparation method thereof.
Background
Ammonia gas has the advantages of high hydrogen density, low liquefaction pressure, no carbon emission and the like, is widely used as an important energy carrier, a fertilizer precursor and a fuel, and plays an important role in both industry and agriculture. Currently, the synthesis of ammonia is carried out by the Haber-Bosch method and the electrocatalytic nitrogen reduction method. However, the Haber-Bosch process is known as an energy intensive industry, involves harsh conditions (typically 300-500 ℃ and 200-300 atm), and its synthesis consumes 1-2% of the energy worldwide per year. Furthermore, H2The raw material is necessary, which results in the consumption of non-renewable resources, CO2The increase in emissions causes serious environmental problems. The electrocatalysis of nitrogen reduction to synthesize ammonia gas requires that solar energy, wind energy and tidal energy are converted into electric energy, and then the nitrogen fixation process can be realized through the electrocatalysis process.
Compared with the two methods, the method for reducing the nitrogen into the ammonia gas by using the semiconductor photocatalysis is a novel method with the lowest cost. Photocatalysis takes clean and energy-rich solar energy as a driving force, takes water and nitrogen as raw materials, and can promote the conversion of the nitrogen into ammonia gas at room temperature and normal pressure. Since N.ident.N cleavage is very difficult, N is formed2+e-+H+→N2The critical step of H requires about 3eV of energy, resulting in TiO2And the production efficiency of converting nitrogen into ammonia under the catalysis of semiconductor materials is extremely low. The hydrogen-terminated diamond semiconductor is an ideal semiconductor material for generating ammonia gas by photocatalysis of nitrogen, the conduction band edge of the hydrogen-terminated diamond semiconductor is 0.8-1.3 eV, and the conduction band edge is positioned above the vacuum level, so that the hydrogen-terminated diamond semiconductor can freely emit electrons into a solution.
However, the band gap of the existing hydrogen-terminated diamond semiconductor is as wide as 5.45eV, and only light with a wavelength less than 225nm can excite electrons. Due to the action of ozone, only 300-400 nm ultraviolet rays from solar radiation can pass through the atmosphere to reach the ground, so that the available light sources of the hydrogen-terminated diamond semiconductor are less, and the photocatalysis cost is higher.
Disclosure of Invention
The invention aims to overcome the defect of high photocatalytic cost of a hydrogen-terminated diamond semiconductor in the prior art, and provides a nitrogen-doped hydrogen-terminated diamond and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
in a first aspect of the present invention, a method for preparing a nitrogen-doped hydrogen-terminated diamond comprises the steps of:
performing nucleation on the pretreated substrate; and then growing a nitrogen-doped polycrystalline diamond layer on the nucleated substrate by a microwave plasma chemical vapor deposition method, and carrying out hydrogenation treatment on the nitrogen-doped polycrystalline diamond layer to obtain the nitrogen-doped hydrogen-terminated diamond.
The preparation method of the nitrogen-doped hydrogen terminal diamond further improves the following steps:
the specific method of the pretreatment comprises the following steps: polishing a single surface or double surfaces of the substrate, sequentially performing ultrasonic treatment in acetone, alcohol and deionized water, and then blowing the substrate by using nitrogen with the purity of not less than 99.999 percent.
The specific method for carrying out nucleation comprises the following steps: the nucleation is carried out by a nano diamond powder dispersion liquid ultrasonic treatment nucleation method or a negative bias nucleation method.
When the nitrogen-doped polycrystalline diamond layer grows on the nucleated substrate by the microwave plasma chemical vapor deposition method, the growth parameters are as follows: the total gas flow is 500-1000 sccm, CH4/H2Gas flow rate ratio of 1-20%, N2/H2The ratio of (A) to (B) is 0.1-10%, the pressure of the cavity is 100-150 Torr, and the growth temperature is 800-1050 ℃.
The specific method for carrying out hydrogenation treatment on the nitrogen-doped polycrystalline diamond layer comprises the following steps: the nitrogen doped polycrystalline diamond layer was subjected to a hydrogenation treatment by an MPCVD apparatus.
Further comprising: the substrate is stripped from the nitrogen doped hydrogen terminated diamond.
In a second aspect of the invention, a nitrogen-doped hydrogen-terminated diamond comprises a hydrogen-terminated polycrystalline diamond; the polycrystalline diamond with hydrogen terminal is doped with nitrogen atoms with the doping concentration of more than or equal to 1017cm-3And the doped nitrogen atoms form nitrogen vacancy color center defects in the hydrogen-terminated polycrystalline diamond; the two-dimensional cavity gas density of the hydrogen-terminated polycrystalline diamond is more than or equal to 1010cm-2。
The nitrogen-doped hydrogen-terminated diamond of the invention is further improved in that:
the grain size of the hydrogen-terminated polycrystalline diamond is less than or equal to 100 mu m, the diameter of the hydrogen-terminated polycrystalline diamond is more than or equal to 1 inch, and the thickness of the hydrogen-terminated polycrystalline diamond is more than or equal to 100 nm.
Also included is a substrate, the hydrogen-terminated polycrystalline diamond disposed over the substrate.
The substrate is made of Si, Mo, W or sapphire.
Compared with the prior art, the invention has the following beneficial effects:
the nitrogen-doped hydrogen terminal diamond of the invention utilizes the characteristic of nitrogen-doped diamond nitrogen vacancy color center defect energy level to make the nitrogen-doped diamond carry out electron transition under the condition of visible light illumination, thereby solvated electrons are taken as a reducing agent to enter solution to participate in nitrogen reduction, and simultaneously utilizes the characteristic of high specific surface area of polycrystalline diamond to increase the quantity of surface solvated electrons and improve the yield of ammonia. And moreover, the cost is greatly reduced by adopting cheaper materials such as polycrystalline diamond and the like. Compared with the current commercial Haber-Bosch process for ammonia synthesis, the method overcomes the disadvantages of using fossil fuel and has high reaction conditions, such as high temperature (C: (A))>300 deg.C, high pressure: (>10MPa), huge process energy consumption and large greenhouse gas emission (per 8 NH)3Emission of 3CO2) And the like. Compared with the alternative schemes developed at present, such as biological nitrogen fixation (imitating a natural method of nitrogen fixation), electrochemical and photochemical reduction processes and the like, the nitrogen-doped hydrogen-terminated diamond does not need to be attached to the surface of a catalyst during the nitrogen reduction reaction, overcomes the defect that the dissolved nitrogen concentration is far lower than the proton concentration in an electrolyte and further the catalytic efficiency is lower than the hydrogenation reaction, further increases the efficiency of the nitrogen fixation reaction, has great influence on the production of nitrogen fertilizers and alternative hydrogen-rich fuels, and provides a way for improving the food and energy production and environmental sustainability.
Drawings
FIG. 1 is a schematic view of a nitrogen doped hydrogen terminated diamond structure with a substrate according to the present invention;
figure 2 is a schematic view of the nitrogen doped hydrogen terminated diamond structure without a substrate according to the present invention.
Wherein: 1-a substrate; 2-polycrystalline diamond; 3-nitrogen atom; 4-hydrogen atom.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, in an embodiment of the present invention, in order to improve the catalytic efficiency of the hydrogen-terminated diamond semiconductor, a nitrogen impurity level is introduced to expand the operating wavelength range of the hydrogen-terminated diamond semiconductor; meanwhile, the diamond is prepared into a polycrystalline form, so that the specific surface area can be increased, the ammonia production efficiency is also improved, and the preparation method of the nitrogen-doped hydrogen-terminated diamond comprises the following steps.
S1: nucleation is performed on the pretreated substrate.
Specifically, the pretreatment method specifically comprises the following steps: polishing the single side or double side of the substrate, sequentially performing ultrasonic treatment in acetone, alcohol and deionized water, and then treating with high-purity nitrogen (O) with purity of not less than 99.999%2Purity of less than or equal to 0.001%) and drying.
Wherein, the material of the substrate can be selected from Si, Mo, W or sapphire.
The specific method for carrying out nucleation comprises the following steps: the nucleation is carried out by a nano diamond powder dispersion liquid ultrasonic treatment nucleation method or a negative bias nucleation method.
In the ultrasonic treatment nucleation method of the nano-diamond powder dispersion, all substrate samples are subjected to ultrasonic treatment for 15 minutes in 0.3g of nano-diamond particles (the diameter of the nano-diamond particles is 5-8 nm) and 20mL of ethanol solution by adopting a nano-diamond powder dispersion ultrasonic treatment mode generally so as to realize high nucleation density.
The negative bias nucleation method comprises the following specific implementation processes: during the nucleation period of diamond, the substrate is negatively biased, i.e., the substrate surface is subjected to a negatively biased pre-deposition process with high carbon source concentration and low reaction pressure, in CH4/H2As reaction gas, the substrate is a single crystal Si (100) surface, the substrate temperature is 900 deg.C when CH4The concentration is 1% -40%, the reaction pressure is 2X 10Pa, when the substrate is applied with negative bias (0-200V), the nucleation density of diamond is enhanced in different degrees in the nucleation period, and the enhancement effect is along with CH4The concentration is increased and the negative bias value is increased, then the negative bias is removed, and the concentration of the carbon source in the reaction gas and the reaction pressure are adjusted to be the normal condition for growing the diamond film, namely entering the growth period.
S2: a nitrogen doped polycrystalline diamond layer was grown on the nucleated substrate by a microwave plasma chemical vapour deposition method.
In particular, nitrogen-doped polycrystalline diamond layers of different thicknesses were grown on nucleated substrates by Microwave Plasma Chemical Vapour Deposition (MPCVD) using a modified AsTex system (Carat Systems).
Wherein, when the polycrystalline diamond layer doped with nitrogen grows, the growth parameters are as follows: the total gas flow is 500-1000 sccm, CH4/H2Gas flow rate ratio of 1-20%, N2/H2The ratio of (A) to (B) is 0.1-10%, the pressure of the cavity is 100-150 Torr, and the growth temperature is 800-1050 ℃.
S3: and (4) carrying out hydrogenation treatment on the nitrogen-doped polycrystalline diamond layer to obtain the nitrogen-doped hydrogen terminal diamond.
Specifically, after the growth is finished, the substrate is taken out and exposed to the air for 60min, and the surface hydrogen termination is waited to be generated. The specific method for carrying out hydrogenation treatment on the nitrogen-doped polycrystalline diamond layer comprises the following steps: the nitrogen doped polycrystalline diamond layer was subjected to a hydrogenation treatment by an MPCVD apparatus.
Referring to fig. 2, after obtaining the nitrogen-doped hydrogen-terminated diamond, it is preferable to further include: the substrate is stripped from the nitrogen doped hydrogen terminated diamond. That is, the nitrogen-doped hydrogen-terminated diamond produced by the method may be a polycrystalline diamond film with a substrate as shown in FIG. 1, or may be a self-supporting polycrystalline diamond wafer that has been peeled off from the substrate as shown in FIG. 2.
In another embodiment of the present invention, a nitrogen-doped hydrogen-terminated diamond is provided, which may be prepared by the method for preparing a nitrogen-doped hydrogen-terminated diamond of the above embodiment, and specifically, the nitrogen-doped hydrogen-terminated diamond includes a hydrogen-terminated polycrystalline diamond, the hydrogen-terminated polycrystalline diamond is doped with nitrogen atoms, and in order to ensure that the nitrogen-doped hydrogen-terminated diamond has a relatively high responsivity under visible light, the doping concentration of the nitrogen atoms is greater than or equal to 1017cm-3And the doped nitrogen atoms form nitrogen vacancy color center defects in the hydrogen terminal polycrystalline diamond, so that the spectral response range of the nitrogen-doped hydrogen terminal diamond is further expanded. Meanwhile, the number of surface hydrogen atoms affects the ability to give solvated electrons, and thus polycrystalline diamond is prepared, increasing the specific surface area, and thus increasing the number of surface hydrogen atoms. Although the number of hydrogen atoms cannot be measuredHowever, since the number of hydrogen atoms is directly correlated with the concentration of the two-dimensional cavity gas on the surface, whether the number of hydrogen atoms is proper or not can be judged by the concentration of the two-dimensional cavity gas, and specifically, the two-dimensional cavity gas density of the hydrogen-terminated polycrystalline diamond is more than or equal to 1010cm-2。
Preferably, the grain size of the hydrogen-terminated polycrystalline diamond is less than or equal to 100 μm, the diameter of the hydrogen-terminated polycrystalline diamond is greater than or equal to 1 inch, and the thickness of the hydrogen-terminated polycrystalline diamond is greater than or equal to 100 nm.
Preferably, the hydrogen-terminated polycrystalline diamond further comprises a substrate, the hydrogen-terminated polycrystalline diamond being disposed over the substrate.
Several specific examples are described below to illustrate the method of producing nitrogen-doped hydrogen-terminated diamond and the ammonia production efficiency of nitrogen-doped hydrogen-terminated diamond according to the present invention.
Example 1
And carrying out nucleation on the pretreated substrate, then growing a nitrogen-doped polycrystalline diamond layer on the nucleated substrate by a microwave plasma chemical vapor deposition method, and carrying out hydrogenation treatment on the nitrogen-doped polycrystalline diamond layer to obtain the nitrogen-doped hydrogen-terminated diamond. Wherein, when the nitrogen-doped polycrystalline diamond layer grows on the nucleated substrate by a microwave plasma chemical vapor deposition method, the growth parameters are as follows: the total flow rate of the growth gas is 500sccm, CH4/H2The ratio is 4%, the gas pressure is 90Torr, the growth temperature is 950 ℃, the microwave power is 2000W, and N is2/H2The ratio is 1%. The thickness of the prepared nitrogen-doped hydrogen-terminated diamond is about 200nm, and the average diameter of the crystal grains of the hydrogen-terminated polycrystalline diamond is 20 nm. Performing linear regression fitting by using a least square method, wherein the average rate of the catalytic nitrogen of the nitrogen-doped hydrogen-terminated diamond prepared by the method is 9.825 +/-1.32 nmol/cm2·h。
Example 2
The difference compared to example 1 is that when growing a nitrogen doped polycrystalline diamond layer on a nucleated substrate by a microwave plasma chemical vapour deposition process, the growth parameters were: the total flow of growth gas is 1000sccm, CH4/H2The ratio is 6%,the gas pressure is 100Torr, the growth temperature is 1000 ℃, the microwave power is 2000W, and N is2/H2The ratio was 3%. The thickness of the prepared nitrogen-doped hydrogen-terminated diamond was about 200nm, and the average diameter of the crystal grains of the hydrogen-terminated polycrystalline diamond was 2 μm. Performing linear regression fitting by using a least square method, wherein the average rate of the catalytic nitrogen of the nitrogen-doped hydrogen-terminated diamond prepared by the method is 6.42 +/-1.39 nmol/cm2·h。
Example 3
The difference compared to example 1 is that when growing a nitrogen doped polycrystalline diamond layer on a nucleated substrate by a microwave plasma chemical vapour deposition process, the growth parameters were: the total flow of the growth gas is 800sccm, CH4/H2The ratio is 10%, the gas pressure is 120Torr, the growth temperature is 1000 deg.C, the microwave power is 2000W, and N is2/H2The ratio was 7%. The thickness of the prepared nitrogen-doped hydrogen-terminated diamond was about 200nm, and the average diameter of the crystal grains of the hydrogen-terminated polycrystalline diamond was 25 μm. Performing linear regression fitting by using a least square method, wherein the average rate of the catalytic nitrogen for preparing the nitrogen-doped hydrogen-terminated diamond is 2.45 +/-0.17 nmol/cm2·h。
Example 4
The difference compared to example 1 is that when growing a nitrogen doped polycrystalline diamond layer on a nucleated substrate by a microwave plasma chemical vapour deposition process, the growth parameters were: the total flow of the growth gas is 700sccm, CH4/H2The ratio is 20%, the gas pressure is 150Torr, the growth temperature is 1050 ℃, the microwave power is 2000W, and N is2/H2The ratio is 10%. The thickness of the prepared nitrogen-doped hydrogen-terminated diamond was about 200nm, and the average diameter of the crystal grains of the hydrogen-terminated polycrystalline diamond was 40 μm. Performing linear regression fitting by using a least square method, wherein the average rate of the catalytic nitrogen of the nitrogen-doped hydrogen-terminated diamond prepared by the method is 1.57 +/-0.18 nmol/cm2·h。
Meanwhile, nitrogen fixation reaction is mainly carried out by means of a noble metal catalyst, a non-noble metal catalyst, a monoatomic catalyst, a carbon-based material catalyst and the like at present, and TiO is particularly adopted2Modified forms of (2) and some clustered sulfides, e.g. MO2Fe6S8-Sn2S6. However, since the intermediates and products are bound by deep valence bands, re-oxidation is required and absorption at the reactant surface is weak, N in the visible region2The fixation rate is lower than 67 percent, and experiments prove that ZrO after 1 hour of visible light irradiation2And TiO2The reduction efficiencies of (a) were 16.8% and 18.1%, respectively; in addition, the nano Au is subjected to performance study in 0.1MHCl solution, and the ammonia yield is 25.57 mu gh at the voltage of-0.20 VvsRHE-1mg-1(ii) a The MoS loaded with Fe monoatomic atoms is obtained by a simple hydrothermal post-liquid-phase control loading method2Catalyst at 0.5MK2SO4The catalyst had an ammonia yield of 8.63 μ gh at-0.30 VvsRHE in the electrolyte-1mg-1。
And with reference to examples 1 to 4 above, the maximum average rate of catalytic nitrogen gas for nitrogen-doped hydrogen-terminated diamond was 9.825 + -1.32 nmol/cm2H, minimum mean rate of 1.57. + -. 0.18nmol/cm2H, greatly improving the efficiency of catalyzing nitrogen, namely greatly improving the ammonia production efficiency.
The excellent ammonia generating performance of the nitrogen-doped diamond film is attributed to the existence of NV color centers, which can increase the light absorption in visible light and ultraviolet regions, and the characteristic of hydrogen terminals enables electrons to enter a solution without potential barriers, so that the number of solvated electrons is increased, more electrons are provided for nitrogen reduction, and the ammonia generating efficiency is improved.
Based on the average diameter of crystal grains of the hydrogen terminal nitrogen-doped polycrystalline diamond, the smaller the average diameter is, the larger the contact specific surface area is, the faster the reaction rate is, nitrogen vacancy defects can be utilized to carry out catalytic reduction on nitrogen under the illumination condition, the polycrystalline diamond is cheap, the cost is greatly reduced, no renewable resources are consumed and discharged in the catalytic process, the polycrystalline diamond is green and environment-friendly, and the sustainable development is promoted.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing a nitrogen-doped hydrogen-terminated diamond, comprising the steps of:
performing nucleation on the pretreated substrate; and then growing a nitrogen-doped polycrystalline diamond layer on the nucleated substrate by a microwave plasma chemical vapor deposition method, and carrying out hydrogenation treatment on the nitrogen-doped polycrystalline diamond layer to obtain the nitrogen-doped hydrogen-terminated diamond.
2. The method of making a nitrogen-doped hydrogen-terminated diamond according to claim 1, wherein the pre-treatment is performed by:
polishing a single surface or double surfaces of the substrate, sequentially performing ultrasonic treatment in acetone, alcohol and deionized water, and then blowing the substrate by using nitrogen with the purity of not less than 99.999 percent.
3. The method of making a nitrogen doped hydrogen-terminated diamond according to claim 1, wherein the specific method of nucleation is:
the nucleation is carried out by a nano diamond powder dispersion liquid ultrasonic treatment nucleation method or a negative bias nucleation method.
4. The method of making a nitrogen doped hydrogen terminated diamond according to claim 1, wherein when growing a nitrogen doped polycrystalline diamond layer on a nucleated substrate by a microwave plasma chemical vapor deposition process, the growth parameters are: the total gas flow is 500-1000 sccm, CH4/H2Gas flow rate ratio of 1-20%, N2/H2The ratio of (A) to (B) is 0.1-10%, the pressure of the cavity is 100-150 Torr, and the growth temperature is 800-1050 ℃.
5. The method of making a nitrogen-doped hydrogen-terminated diamond according to claim 1, wherein the specific method of hydrotreating the nitrogen-doped polycrystalline diamond layer is:
the nitrogen doped polycrystalline diamond layer was subjected to a hydrogenation treatment by an MPCVD apparatus.
6. The method of making a nitrogen-doped hydrogen-terminated diamond according to claim 1, further comprising: the substrate is stripped from the nitrogen doped hydrogen terminated diamond.
7. A nitrogen doped hydrogen-terminated diamond comprising a hydrogen-terminated polycrystalline diamond;
the polycrystalline diamond with hydrogen terminal is doped with nitrogen atoms with the doping concentration of more than or equal to 1017cm-3And the doped nitrogen atoms form nitrogen vacancy color center defects in the hydrogen-terminated polycrystalline diamond;
the two-dimensional cavity gas density of the hydrogen-terminated polycrystalline diamond is more than or equal to 1010cm-2。
8. The nitrogen-doped hydrogen-terminated diamond according to claim 7, wherein the hydrogen-terminated polycrystalline diamond has a grain size of 100 μm or less, a diameter of 1 inch or more, and a thickness of 100nm or more.
9. The nitrogen-doped hydrogen-terminated diamond according to claim 7, further comprising a substrate, the hydrogen-terminated polycrystalline diamond being disposed over the substrate.
10. The nitrogen-doped hydrogen-terminated diamond according to claim 9, wherein the substrate is Si, Mo, W or sapphire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110821200.3A CN113731459A (en) | 2021-07-20 | 2021-07-20 | Nitrogen-doped hydrogen terminal diamond and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110821200.3A CN113731459A (en) | 2021-07-20 | 2021-07-20 | Nitrogen-doped hydrogen terminal diamond and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113731459A true CN113731459A (en) | 2021-12-03 |
Family
ID=78728781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110821200.3A Pending CN113731459A (en) | 2021-07-20 | 2021-07-20 | Nitrogen-doped hydrogen terminal diamond and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113731459A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114646624A (en) * | 2022-03-24 | 2022-06-21 | 东南大学 | Fluorescence regulation and control method for diamond NV color center |
| CN114717534A (en) * | 2022-03-29 | 2022-07-08 | 北京科技大学 | Preparation method of large-area ultra-high-hardness diamond film |
| WO2024219291A1 (en) * | 2023-04-18 | 2024-10-24 | 株式会社ダイセル | Semiconductor catalyst, catalyst electrode, method for producing reduced product, and device for producing reduced product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142313A (en) * | 2018-08-03 | 2019-01-04 | 吉林大学 | The diamond substrate and preparation method thereof of semiconductor surface enhancing Raman scattering |
| CN110560034A (en) * | 2019-08-30 | 2019-12-13 | 深圳先进技术研究院 | boron-doped diamond-loaded metal monoatomic atom and preparation method and application thereof |
-
2021
- 2021-07-20 CN CN202110821200.3A patent/CN113731459A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142313A (en) * | 2018-08-03 | 2019-01-04 | 吉林大学 | The diamond substrate and preparation method thereof of semiconductor surface enhancing Raman scattering |
| CN110560034A (en) * | 2019-08-30 | 2019-12-13 | 深圳先进技术研究院 | boron-doped diamond-loaded metal monoatomic atom and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| RUI SU等: "Visible-Light Activation of Photocatalytic for Reduction of Nitrogen to Ammonia by Introducing Impurity Defect Levels into Nanocrystalline Diamond", 《MATERIALS》, vol. 13, pages 2 - 3 * |
| 张永宏等: "现代薄膜材料与技术", 31 August 2016, pages: 185 - 187 * |
| 王玉乾;王兵;甘孔银;梅军;孙文周;袁庆;燕丽娜;郭娟;: "掺氮对纳米金刚石薄膜形貌及组成结构的影响", 武汉理工大学学报, no. 08, pages 12 * |
| 邵乐喜, 刘小平, 屈菊兰, 谢二庆, 贺德衍, 陈光华: "原位氮掺杂对CVD金刚石薄膜生长和结构的影响", 真空科学与技术学报, no. 03, pages 222 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114646624A (en) * | 2022-03-24 | 2022-06-21 | 东南大学 | Fluorescence regulation and control method for diamond NV color center |
| CN114717534A (en) * | 2022-03-29 | 2022-07-08 | 北京科技大学 | Preparation method of large-area ultra-high-hardness diamond film |
| CN114717534B (en) * | 2022-03-29 | 2022-12-30 | 北京科技大学 | Preparation method of large-area ultrahigh-hardness diamond film |
| WO2024219291A1 (en) * | 2023-04-18 | 2024-10-24 | 株式会社ダイセル | Semiconductor catalyst, catalyst electrode, method for producing reduced product, and device for producing reduced product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113731459A (en) | Nitrogen-doped hydrogen terminal diamond and preparation method thereof | |
| He et al. | Thin film photoelectrodes for solar water splitting | |
| KR100759547B1 (en) | Carbon nanotube for fuel cell, method for preparing the same and fuel cell using the carbon nanotube | |
| Oh et al. | Atomic layer deposited molybdenum disulfide on Si photocathodes for highly efficient photoelectrochemical water reduction reaction | |
| Kang et al. | Low temperature fabrication of Fe 2 O 3 nanorod film coated with ultra-thin gC 3 N 4 for a direct z-scheme exerting photocatalytic activities | |
| CN112354553B (en) | g-C 3 N 4 Preparation method of base p-n homojunction photocatalyst and preparation method of hydrogen | |
| CN109402653B (en) | InGaN nano-pillar@Au nano-particle composite structure on Si substrate and preparation method and application thereof | |
| CN111005035B (en) | Preparation method and application of integrated electrode containing iron-nickel doped tantalum nitride carbon nano film | |
| CN105401150A (en) | TiO2 nano-beam/boron-doped diamond film composite photoelectrocatalysis electrode and preparation method and application thereof | |
| CN109161850B (en) | (In) GaN nanotube growing on Si substrate and preparation method and application thereof | |
| CN114657641A (en) | Annealed Si-based InN nano-column heterojunction and preparation method and application thereof | |
| CN109207958B (en) | A kind of preparation method of the phosphating sludge nano-chip arrays structure perpendicular to substrate grown | |
| US10697073B2 (en) | Method for manufacturing electrode for hydrogen production using tungsten carbide nanoflake and electrode for hydrogen production manufactured thereby | |
| CN111036263B (en) | InGaN nanorod @ Ti-Ni nanoparticle composite structure on Si substrate and preparation method and application thereof | |
| CN111804317A (en) | Method for directly growing high-density cobalt phosphide nano-wire electrocatalyst on conductive substrate and application thereof | |
| KR100459060B1 (en) | Manufacturing method of Pt catalyst for electrode utilizing carbon nanotube | |
| CN108246287B (en) | Preparation method of double-quantum-dot modified flower-like three-dimensional graphene and photocatalytic material | |
| CN113862720A (en) | Metal Cu thin film electrode capable of selectively exposing (100) crystal face and preparation method thereof | |
| CN108642517B (en) | Method for growing high-density boundary molybdenum disulfide nano material by using photinia serrulata | |
| CN115430447B (en) | Preparation method and application of Rh nanoparticle modified III-nitride Si catalyst | |
| CN116588930B (en) | Artificial diamond and preparation method and application thereof | |
| CN115364887B (en) | Preparation method and application of Au-In binary nano promoter loaded III-group nitride | |
| WO2023238387A1 (en) | Nitride semiconductor photoelectrode and production method therefor | |
| KR102671960B1 (en) | Photoelectrochemical photoelectrode device with a wide bandgap and a Hydrogen Generator Including the Same | |
| KR102483058B1 (en) | Manufacturing method of bimetallic transition metal nitride, the bimetallic transition metal nitride manufactured thereby and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |