CN113385206A - High-efficiency hydrogen production catalyst under strong interaction of metal carriers and preparation method - Google Patents
High-efficiency hydrogen production catalyst under strong interaction of metal carriers and preparation method Download PDFInfo
- Publication number
- CN113385206A CN113385206A CN202110652199.6A CN202110652199A CN113385206A CN 113385206 A CN113385206 A CN 113385206A CN 202110652199 A CN202110652199 A CN 202110652199A CN 113385206 A CN113385206 A CN 113385206A
- Authority
- CN
- China
- Prior art keywords
- mxene
- alk
- catalyst
- solution
- hydrogen
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000001257 hydrogen Substances 0.000 title claims abstract description 72
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 230000003993 interaction Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 239000000969 carrier Substances 0.000 title claims abstract description 11
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 60
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 claims abstract description 24
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 238000006557 surface reaction Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 241000446313 Lamella Species 0.000 abstract 1
- 239000012798 spherical particle Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- 238000011068 loading method Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/393—
-
- B01J35/50—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a catalyst for hydrogen production by hydrolysis under strong interaction of metal carriers and a preparation method thereof. The invention solves the problems of low hydrogen production efficiency and high catalyst cost of ammonia borane catalyzed by a Pd-based catalyst. alk-Ti of the invention3C2The MXene-Pd supported catalyst is prepared from alkalified two-dimensional layered Ti3C2MXene and nano spherical particle Pd elementary substance loaded on the lamella. The method comprises the following steps: reacting alk-Ti3C2MXene dispersed in CH3OH in, and Pd (OAc)2CH (A) of3Mixing OH solution, and stirring continuously to make Pd ions fully adsorbed and anchored on alk-Ti3C2MXene surface, and reduction reaction occurs. After the reaction is finished, carrying out centrifugal separation and drying to obtain alk-Ti with strong interaction of metal carriers3C2MXene-Pd supported catalyst. The invention provides alk-Ti which is simple to operate, mild in condition, environment-friendly, low in synthesis temperature and easy to produce in large scale3C2MXene-based composite catalyst.
Description
Technical Field
The invention relates to the field of hydrogen energy, in particular to alk-Ti3C2A preparation method of MXene composite supported catalyst and the field of ammonia borane hydrolysis hydrogen production.
Background
Energy is the basis of social development, and along with the improvement of living standard of people, the demand on energy is increasing day by day. Because conventional fossil fuels have a limited reserve and pose serious environmental problems, it is becoming important to find new clean renewable energy sources. Among them, hydrogen is attracting attention because of its advantages such as environmental friendliness of products and high energy density. However, how to safely and effectively store and transport hydrogen is an urgent problem to be solved. Among the common hydrogen storage materials, ammonia borane (NH)3BH3) The mass hydrogen storage density is 19.6%, the stability at room temperature is good, the hydrolysis hydrogen production device is safe and convenient, and the hydrolysis hydrogen production device is a suitable hydrogen production material. The hydrogen production by ammonia borane has three modes, namely solid-state thermal decomposition, alcoholysis and hydrolysis. Compared with pyrolysis and alcoholysis hydrogen production, hydrolysis hydrogen production can be carried out under the conditions of normal temperature and normal pressure by using catalyst catalysis, and the method has the advantages of low cost, high hydrogen release rate, cleanness, no pollution and the like. In aqueous solution, ammonia borane molecules are adsorbed on the surface of the catalyst, B-N bonds are broken under the attack of water molecules, and H in the ammonia borane is combined with H in the water molecules to form H2. Noble metals (e.g., Pt, Pd, Ru) have been the most prominent catalysts for catalytic hydrogen production to date, however, their high cost and scarcity have limited their use in practical production. In order to reduce the use amount and reduce the cost, the design of the catalyst is more inclined to be in a supported type. And the carrier material in the supported catalyst plays an important role in catalyzing the ammonia borane decomposition hydrogen production mechanism. The texture characteristics of the carrier determine the particle size and distribution of the noble metal, and the strong interaction between the carrier and the noble metal nano particles can more effectively improve the performance of ammonia borane decomposition hydrogen production. The Pd in the prior noble metal catalyst has wide application and higher catalytic activity to ammonia borane, but has the defects of larger prepared particle size and easy agglomeration, which causes the reduction of the catalytic activity,it is important to select a suitable support material, which is a conventional carbon-based support material that has good electrical conductivity but poor stability and lacks more efficient interaction between the support and the catalyst during the catalytic process.
Since the first MXene reported in 2011, MXene has become a promising two-dimensional material, which is a two-dimensional transition metal carbide or nitride crystal with a thickness of only a single atom or a few atoms and has a chemical formula of Mn+1Xn(n ═ 1, 2, 3, M is a transition metal element, and X is carbon or a nitrogen element). The MX two-dimensional crystal is obtained by removing an element A from ternary layered ceramic MAX, wherein the element A is generally silicon or aluminum. Wherein the Ti group MXene (Ti)3C2MXene), it has the advantages of fast electron transfer rate, strong interface interaction, etc. At present, Ti3C2MXene is mainly applied to the fields of electrochemical oxidation and sensor detection.
Disclosure of Invention
The invention aims to solve the problems of high cost, low activity and the like of Pd noble metal as a catalyst in the using process, overcomes the difficulties that in the prior art, the size of Pd loaded particles on most carriers is large, the Pd loaded particles lack interaction with the carriers to enhance the catalytic effect and the Pd noble metal cannot be efficiently utilized, and provides alk-Ti under the strong interaction of metal carriers3C2MXene-Pd supported catalyst and its preparation process. The inventor of the application carries out a large number of experiments, changes the dosage and synthesis conditions of Pd through research and calculation on the interaction between the carrier and metal Pd, and finally finds out a catalyst with strong interaction and enhanced catalytic effect of the metal carrier, and the catalytic conversion efficiency (TOF) value is as high as 230.6min-1The ammonia borane hydrolysis hydrogen production catalyst.
Specifically, the invention provides a high-efficiency ammonia borane hydrolysis hydrogen production catalyst under strong interaction of metal carriers, which is characterized in that the catalyst is alk-Ti3C2MXene-Pd supported catalyst, which is prepared from two-dimensional layered material alk-Ti3C2MXene and granular Pd elementary substance supported on a sheet layer, wherein alk-Ti3C2The mass ratio of MXene to Pd is 1: 0.005 to 1: 0.24.
alk-Ti of the invention3C2By adjusting the dosage of Pd in the MXene-Pd supported catalyst, the size and dispersion degree of Pd particles can be regulated and controlled, the catalytic activity of Pd (for ammonia borane catalytic hydrogen production) is optimized, and alk-Ti with optimal performance is obtained3C2MXene-Pd supported catalyst.
The invention also provides a method for preparing the hydrogen catalyst, which is characterized by comprising the following steps:
(1) weighing alk-Ti3C2MXene、Pd(OAc)2、CH3OH, wherein alk-Ti3C2MXene and Pd (OAc)2The mass ratio of (1): (0.01 to 0.24),
(2) according to alk-Ti3C2MXene and CH3The mass ratio of OH is 1: (92 to 68) adding alk-Ti3C2MXene dispersed in CH3In OH, stirring to give a solution A according to Pd (OAc)2And CH3The mass ratio of OH is 1: (1240 to 62) Pd (OAc)2Is dispersed in CH3In OH, stirring to obtain a solution B;
(3) uniformly mixing the solution A and the solution B, and continuously stirring to ensure that Pd is contained2+Ions are fully adsorbed on alk-Ti3C2MXene surface and reduction reaction;
(4) after the reaction is finished, carrying out centrifugal separation and drying to obtain alk-Ti3C2MXene-Pd hydrogen producing catalyst.
Wherein alk-Ti described in step (1)3C2The preparation method of MXene comprises the following steps:
(1.1) measuring 20-30 mL of concentrated hydrofluoric acid with the mass percentage concentration of 49% in a tetrafluoroethylene plastic cup, and stirring 1-1.5 g of Ti3AlC2Adding the mixture into hydrofluoric acid, and stirring and reacting for 24-48 h at 40-60 ℃; after the reaction is finished, the solution is centrifugally separated, and solid-phase substances are washed by deionized water until the pH value of the supernatant is reached>6, continuing centrifugal separation;
(1.2) dispersing the solid phase in deionized water under argonUnder the protection of gas, performing ultrasonic treatment for 1-2 h, centrifuging to obtain a precipitate, and freeze-drying the precipitate to obtain Ti with a lamellar structure3C2MXene。
(1.3) adding 0.5 to 1g of Ti3C2MXene is dispersed in 50-200 mL of NaOH solution with the molar concentration of 0.5-3 mol/L for alkalization treatment, stirred at 25-60 ℃ for 2-4 h, then washed by deionized water until the pH value of the supernatant is 7, centrifugally separated and dried to obtain alk-Ti3C2MXene。
In another aspect, the invention provides alk-Ti under strong interaction of metal carriers3C2Use of MXene-Pd supported catalysts, characterized in that alk-Ti3C2The MXene-Pd supported catalyst is used for catalyzing ammonia borane hydrolysis hydrogen production process, and the application comprises the following steps: (1) reacting alk-Ti3C2Placing MXene-Pd supported catalyst in a flask, and mixing with deionized water uniformly by ultrasonic; (2) preparing ammonia borane alkaline solution; (3) adding the solution prepared in the step (2) into the solution prepared in the step (1).
More specifically, the application method is as follows: the prepared alk-Ti3C2MXene-Pd supported catalyst is used as catalyst for producing hydrogen by hydrolyzing ammonia borane, the solvent is deionized water, and hydrogen is collected by adopting a drainage gas collection method.
Putting 50mg of catalyst into a round-bottom flask, adding 5mL of deionized water, performing ultrasonic treatment for 2min, putting the flask into a water bath kettle at 25 ℃ for preheating, wherein the rotating speed of a magnetic stirrer is 450 r/min. 0.2g of NaOH is placed in a beaker, 5mL of deionized water is added, ultrasonic treatment is carried out until the NaOH solution is completely dissolved, 31.8mg of ammonia borane is added into the NaOH solution, and the beaker is shaken to completely dissolve the ammonia borane. The solution was added to a round bottom flask and hydrogen was collected by draining gas. And when the first bubble emerges from the air outlet, timing is started, and timing is carried out once every 5mL until the reaction is finished.
Technical effects
The inventor of the application discovers that the two-dimensional material Ti is obtained through the simulation of the density functional theory3C2MXene and noble metal Pd can generate strong interaction, and the carrier and the noble metal can promote each other to enable alk-Ti3C2MXene-Pd exerts a greater catalytic effect overall. And experiments prove that the MXene surface functional group has an anchoring effect on Pd in the reduction process of Pd metal, so that Pd particles growing on the MXene surface have small size, large surface area, uniform dispersion, no agglomeration, huge catalytic surface and Ti3AlC2After being etched by HF, the Al layer is completely stripped to form Ti with a lamellar accordion structure3C2It also provides a large number of loading surfaces for the catalyst. By the method, a large amount of uniformly-loaded Pd particles with the particle size of about 5nm and without agglomeration can be obtained in the composite material, the composite material is used for catalyzing ammonia borane hydrolysis hydrogen production, and experimental results show that the composite material has excellent catalytic activity, and the TOF value reaches 230.6min-1。
The inventor obtains a catalytic mechanism through research and calculation on the interaction between the carrier and the metal Pd, and designs a preparation scheme based on the mechanism to prepare the catalyst of the invention, the carrier and the metal Pd have strong interaction and mutual assistance in the catalytic process, the utilization rate of the Pd is improved, and the cost of the catalyst is effectively reduced.
Drawings
FIG. 1 shows alk-Ti in example 13C2The scanning electron microscope photo of MXene can show Ti3AlC2After being etched by HF, the Al layer is completely stripped to form Ti with a lamellar accordion structure3C2It also provides a large number of loading surfaces for the catalyst.
FIG. 2 shows the matrix materials MXene and alk-Ti in example 13C2X-ray diffraction (XRD) patterns of MXene-Pd supported catalyst, wherein 7.1 °, 18.8 °, 28.3 ° and 60.5 ° correspond to Ti3C2The (002), (004), (006) and (110) crystal planes of MXene, which indicates Ti3C2Were successfully synthesized. No characteristic peak of Pd was observed in XRD due to the lower loading of Pd and smaller particle size.
FIG. 3 shows alk-Ti in example 13C2Transmission Electron Microscope (TEM) image of MXene-supported catalyst, from which Pd particles can be seenThe particles are uniformly dispersed on the carrier material MXene, the particle size is about 5nm, and the agglomeration phenomenon is avoided.
FIG. 4 shows alk-Ti loadings of different amounts in example 13C2The MXene-Pd supported catalyst has the catalytic performance (a) and the corresponding TOF value (b) on the hydrolysis of ammonia borane to produce hydrogen. As can be seen from the graph (a), the ammonia borane hydrolysis hydrogen production time is reduced sequentially along with the increase of the loading amount, wherein the catalytic performance of the catalyst with the loading amount of 0.5 wt.% is poor, and the catalytic hydrogen production is incomplete when 55mL of hydrogen is produced in 50 min. 1. The catalytic performance was better at 5 and 7 wt.%. Comparing the TOF values corresponding to different loadings, the result was that the catalyst was excellent in catalytic performance when the catalyst loading was 1 wt.%, with the TOF value being 230.6min-1The use amount of the noble metal is low, and the application prospect is good.
FIG. 5 is a graph of the catalyst alk-Ti prepared in the present invention for ammonia borane hydrolysis using density functional theory3C2Energy distribution diagram under catalysis of MXene-Pd, compared with that of using the carrier alk-Ti alone3C2MXene, or the energy distribution of Pd alone catalyzed ammonia borane hydrolysis, we can see whether ammonia borane decomposition (FIG. 5-a) or water decomposition (FIG. 5-b) occurs in the catalyst alk-Ti3C2Under MXene-Pd, the activation energy of the reaction is lowest, and the reaction is most easy to occur. Fully proves that Pd and the carrier material alk-Ti3C2The MXene interaction catalyzes the ammonia borane to produce hydrogen.
FIG. 6 shows the hydrogen production effect of the conventional carrier carbon black prepared by the prior method, which is compared with the hydrogen production effect of the common carrier carbon black prepared by the method of the present invention. It can be seen that the catalyst Pd/C prepared by common carrier carbon black loaded Pd is used for catalyzing ammonia borane to produce hydrogen for 20min, the hydrogen production is incomplete, and the catalytic activity is obviously lower than that of the catalyst prepared by the method.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
alk-Ti in the present example3C2MXene-Pd negativeThe preparation method of the supported catalyst comprises the following steps:
one, alk-Ti3C2Preparation of MXene:
(1) 25mL of concentrated hydrofluoric acid with the mass percentage concentration of 49 percent is measured and put in a tetrafluoroethylene plastic cup, and 1.5g of Ti is added under the stirring condition3AlC2Adding into hydrofluoric acid, stirring and reacting for 24h at 60 ℃; after the reaction is finished, the solution is centrifugally separated, and solid-phase substances are washed by deionized water until the pH value of the supernatant is reached>Continuously carrying out centrifugal separation to obtain a solid phase substance;
(2) dispersing the solid phase substance in deionized water, performing ultrasonic treatment for 1h under the protection of argon gas, centrifuging to obtain precipitate, and freeze-drying the precipitate to obtain Ti with lamellar structure3C2MXene。
(3) 0.5g of Ti3C2MXene dispersed in 50mL NaOH solution with molar concentration of 1.5mol/L for alkalization, stirring at 60 deg.C for 4h, washing with deionized water until the pH of the supernatant is 7, centrifuging, and drying to obtain alk-Ti3C2MXene。
Di, alk-Ti3C2Preparation of MXene-Pd supported catalyst
(1) Weighing alk-Ti3C2MXene、Pd(OAc)2、CH3OH, wherein alk-Ti3C2MXene and Pd (OAc)2The mass ratio of (1): 0.02.
(2) according to alk-Ti3C2MXene and CH3The mass ratio of OH is 1: 92, alk-Ti3C2MXene dispersed in CH3Stirring continuously in OH at room temperature to give solution A, according to Pd (OAc)2And CH3The mass ratio of OH is 1: 620, from Pd (OAc)2Is dispersed in CH3Stirring was continued in OH at room temperature to give solution B.
(3) Mixing solution A and solution B at room temperature, and stirring to obtain Pd2+Ions are fully adsorbed on alk-Ti3C2MXene surface, and reduction reaction occurs.
(4) After the reaction is finished, carrying out centrifugal separation and drying to obtain alk-Ti3C2MXene-Pd supported catalyst.
(5) For the prepared alk-Ti3C2The MXene-Pd catalyst is characterized by surface appearance and phase structure:
observing the appearance of the sample by adopting SEM, wherein the specific result is shown in figure 1;
XRD was used for the analysis of the crystalline phase, and the specific results are shown in FIG. 2;
the morphology analysis was performed by TEM, and the specific results are shown in fig. 3.
(6) alk-Ti prepared in this example3C2MXene-Pd supported catalyst is used as catalyst and added into ammonia borane aqueous solution to test the catalytic performance of the catalyst on the hydrogen production by ammonia borane hydrolysis:
alk-Ti prepared by the invention3C2MXene-Pd catalyst 50mg, put in round bottom flask, add 5mL deionized water, ultrasonic for 2min, put in 25 deg.C water bath to preheat, magnetic stirrer speed 450 r/min. 0.2g of NaOH is placed in a beaker, 5mL of deionized water is added, ultrasonic treatment is carried out until the NaOH solution is completely dissolved, 31.8mg of ammonia borane is added into the NaOH solution, and the beaker is shaken to completely dissolve the ammonia borane. The solution was added to a round bottom flask and hydrogen was collected by draining gas. And when the first bubble emerges from the air outlet, timing is started, and timing is carried out once every 5mL until the reaction is finished. The catalytic hydrolysis hydrogen production results and corresponding values are shown in fig. 5 for a 1 wt.% loading sample. As can be seen from fig. 4(a), the ammonia borane hydrolysis hydrogen production time is reduced sequentially with the increase of the loading, wherein the catalyst with the loading of 0.5 wt.% has poor catalytic performance, and 55mL of hydrogen is produced in 59min, and the catalysis is incomplete. 1. The catalytic performances of 5 wt.% and 7 wt.% are better, and the corresponding hydrogen production time is respectively 3.96min, 1.13min and 1.58 min. Comparing the TOF values corresponding to different loadings, the result was that the catalyst was excellent in catalytic performance when the catalyst loading was 1 wt.%, with the TOF value being 230.6min-1The use amount of the noble metal is low, and the application prospect is good.
Example 2
alk-Ti in the present example3C2The preparation method of the MXene-Pd supported catalyst comprises the following steps:
one, alk-Ti3C2Preparation of MXene:
(1) 25mL of concentrated hydrofluoric acid with the mass percentage concentration of 49 percent is measured and put in a tetrafluoroethylene plastic cup, and 1g of Ti is added under the stirring condition3AlC2Adding into hydrofluoric acid, stirring and reacting for 24h at 60 ℃; after the reaction is finished, the solution is centrifugally separated, and solid-phase substances are washed by deionized water until the pH value of the supernatant is reached>Continuously carrying out centrifugal separation to obtain a solid phase substance;
(2) dispersing the solid phase substance in deionized water, performing ultrasonic treatment for 1.5h under the protection of argon gas, centrifuging to obtain precipitate, and freeze-drying the precipitate to obtain Ti with lamellar structure3C2MXene。
(3) 0.5g of Ti3C2MXene dispersed in 50mL NaOH solution with the molar concentration of 1mol/L for alkalization treatment, stirring at 60 ℃ for 4h, then washing with deionized water until the pH of the supernatant is 7, centrifuging, and drying to obtain alk-Ti3C2MXene。
Di, alk-Ti3C2Preparation of MXene-Pd supported catalyst
(1) Weighing alk-Ti3C2MXene、Pd(OAc)2、CH3OH, wherein alk-Ti3C2MXene and Pd (OAc)2The mass ratio of (1): 0.1.
(2) according to alk-Ti3C2MXene and CH3The mass ratio of OH is 1: 92, alk-Ti3C2MXene dispersed in CH3Stirring continuously in OH at room temperature to give solution A, according to Pd (OAc)2And CH3The mass ratio of OH is 1: 124, Pd (OAc)2Is dispersed in CH3Stirring was continued in OH at room temperature to give solution B.
(3) Mixing solution A and solution B at room temperature, and stirring to obtain Pd2+Ions are fully adsorbed on alk-Ti3C2MXene surface, and reduction reaction occurs.
(4) After the reaction is finished, carrying out centrifugal separation and drying to obtain alk-Ti3C2MXene-Pd supported catalyst, the structure of which is the same as the material structure prepared in example 1.
(5) The experiment of hydrogen production by hydrolysis of the prepared catalyst in ammonia borane solution is the same as that of example 1, and the result of hydrogen production by catalysis and the corresponding value are shown as a sample with a load of 5 wt.% in fig. 5. As can be seen from the figure, although this sample used more Pd than 1 wt.% and the TOF value was also lower than 1 wt.% for the sample, 111.6min-1. However, the sample has the shortest hydrogen production time of 1.13min and good hydrogen production effect. Therefore, the scheme of the embodiment is more suitable for the application condition that the hydrogen is required to be rapidly produced, and the hydrogen production time can be greatly shortened.
Comparative examples
In order to compare the hydrogen production effect of the catalyst prepared by the invention, in which the carrier and the metal have strong effects, with the hydrogen production effect of the catalyst Pd/C prepared by the common carrier carbon black, the case that the Pd/C prepared by the existing preparation method is used for ammonia borane catalytic hydrogen production is given in the embodiment.
The preparation method of the Pd/C supported catalyst in this example was carried out according to the following steps:
first, carbon black is commercially available.
Preparation of Pd/C supported catalyst
(1) Weighing carbon Black, Pd (OAc)2、CH3OH, wherein carbon black is reacted with Pd (OAc)2The mass ratio of (1): 0.02.
(2) according to carbon black and CH3The mass ratio of OH is 1: 92, dispersing carbon black in CH3Stirring continuously in OH at room temperature to give solution A, according to Pd (OAc)2And CH3The mass ratio of OH is 1: 620, from Pd (OAc)2Is dispersed in CH3Stirring was continued in OH at room temperature to give solution B.
(3) Mixing solution A and solution B at room temperature, and stirring to obtain Pd2+The ions are fully adsorbed on the surface of the carbon black, and a reduction reaction occurs.
(4) After the reaction is finished, centrifugal separation and drying are carried out to obtain the Pd/C supported catalyst.
(5) The experiment of hydrogen production by hydrolysis of the prepared catalyst in ammonia borane solution is the same as that of example 1, and the result of hydrogen production by catalysis is shown as Pd/C sample in figure 6The product is shown. As can be seen from the figure, alk-Ti in example 13C2An MXene-Pd sample which produces 67mL of hydrogen at 3.96 min; and the Pd/C sample prepared in the comparative example produces 60mL of hydrogen in 20min, and has a slow hydrogen production rate and incomplete hydrogen production. As described above, in the case of one type of catalyst, if the carrier and the catalyst material do not interact with each other, the effect is very undesirable if the hydrogen production reaction is carried out by the action of each catalyst itself. It is therefore particularly important to find support materials capable of interacting, promoting interaction with, alk-Ti3C2MXene can interact with Pd metal in the catalytic process to promote the hydrolysis of ammonia borane to produce hydrogen, so that the hydrogen production efficiency can be greatly improved.
While the principles of the invention have been described in detail in connection with the preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing embodiments are merely illustrative of exemplary implementations of the invention and are not limiting of the scope of the invention. The details of the embodiments are not to be interpreted as limiting the scope of the invention, and any obvious changes, such as equivalent alterations, simple substitutions and the like, based on the technical solution of the invention, can be interpreted without departing from the spirit and scope of the invention.
Claims (9)
1. The catalyst for efficiently catalyzing ammonia borane hydrolysis to produce hydrogen under strong interaction of metal carriers is characterized by being alk-Ti3C2MXene-Pd supported catalyst, which is prepared from two-dimensional layered material alk-Ti3C2MXene and granular Pd elementary substance supported on a sheet layer, wherein alk-Ti3C2The mass ratio of MXene to Pd is 1: 0.005 to 1: 0.24.
2. the catalyst for efficiently catalyzing ammonia borane hydrolysis to produce hydrogen under strong interaction of metal carriers as claimed in claim 1, wherein alk-Ti3C2MXene: the mass ratio of Pd is 1: 0.01 to 1: 0.1.
3. a method for preparing the hydrogen-producing catalyst according to claim 1, characterized by the following steps:
(1) weighing alk-Ti3C2MXene、Pd(OAc)2、CH3OH, wherein alk-Ti3C2MXene and Pd (OAc)2The mass ratio of (1): (0.01 to 0.24);
(2) according to alk-Ti3C2MXene and CH3The mass ratio of OH is 1: (92 to 68) adding alk-Ti3C2MXene dispersed in CH3In OH, stirring to give a solution A according to Pd (OAc)2And CH3The mass ratio of OH is 1: (1240 to 62) Pd (OAc)2Is dispersed in CH3In OH, stirring to obtain a solution B;
(3) uniformly mixing the solution A and the solution B, and continuously stirring to ensure that Pd is contained2+Ions are fully adsorbed on alk-Ti3C2MXene surface and reduction reaction;
(4) after the reaction is finished, carrying out centrifugal separation and drying to obtain alk-Ti3C2MXene-Pd hydrogen producing catalyst.
4. The production method of a hydrogen-producing catalyst according to claim 3,
alk-Ti described in step (1)3C2The preparation method of MXene comprises the following steps:
(1.1) measuring 20-30 mL of concentrated hydrofluoric acid with the mass percentage concentration of 49% in a tetrafluoroethylene plastic cup, and stirring 1-1.5 g of Ti3AlC2Adding the mixture into hydrofluoric acid, and stirring and reacting for 24-48 h at 40-60 ℃; after the reaction is finished, the solution is centrifugally separated, and solid-phase substances are washed by deionized water until the pH value of the supernatant is reached>6, continuing centrifugal separation;
(1.2) dispersing the solid phase substance in deionized water, carrying out ultrasonic treatment for 1-2 h under the protection of argon, centrifuging to obtain a precipitate, and freeze-drying the precipitate to obtain Ti with a lamellar structure3C2MXene；
(1.3) adding 0.5 to 1g of Ti3C2MXene dispersed in 50-200 mL of a solution with a molar concentration of 0.5-3 molAlkalizing in a/L NaOH solution, stirring for 2-4 h at 25-60 ℃, then washing with deionized water until the pH of the supernatant is 7, centrifugally separating, and drying to obtain alk-Ti3C2MXene。
5. The production method of the hydrogen-producing catalyst according to claim 3 or 4, characterized in that, in the step (2), alk-Ti is added3C2MXene dispersed in CH3And in OH, stirring for 10-30 min.
6. The method for producing a hydrogen-producing catalyst according to claim 3 or 4, wherein in the step (2), Pd (OAc)2Is dispersed in CH3In OH, the stirring time was 30 s.
7. An alk-Ti according to claim 3 or 43C2The preparation method of the MXene-Pd supported catalyst is characterized in that in the step (3), the reaction time after the solution A and the solution B are mixed is 0.5-2 h.
8. An alk-Ti according to claim 3 or 43C2The preparation method of MXene-Pd supported catalyst is characterized in that, in the step (4), alk-Ti3C2The drying temperature of the MXene-Pd supported catalyst is 30 ℃ and 12 h.
9. Ammonia borane hydrolysis hydrogen production catalyst alk-Ti under strong interaction of metal carrier3C2Use of MXene-Pd, characterized in that said alk-Ti is3C2The MXene-Pd catalyst is the catalyst described in claim 1, and the catalyst is used for catalyzing and treating ammonia borane hydrolysis hydrogen production process, and the application comprises the following steps: (1) reacting alk-Ti3C2Placing MXene-Pd catalyst in a container, and mixing with deionized water for uniform ultrasonic treatment; (2) preparing ammonia borane alkaline solution; (3) adding the solution prepared in the step (2) into the solution prepared in the step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110652199.6A CN113385206A (en) | 2021-06-11 | 2021-06-11 | High-efficiency hydrogen production catalyst under strong interaction of metal carriers and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110652199.6A CN113385206A (en) | 2021-06-11 | 2021-06-11 | High-efficiency hydrogen production catalyst under strong interaction of metal carriers and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113385206A true CN113385206A (en) | 2021-09-14 |
Family
ID=77620480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110652199.6A Pending CN113385206A (en) | 2021-06-11 | 2021-06-11 | High-efficiency hydrogen production catalyst under strong interaction of metal carriers and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113385206A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959344A (en) * | 2022-06-08 | 2022-08-30 | 郑州大学 | High-strength Ti 3 C 2 T x Magnesium alloy ZK61 and preparation method thereof |
| CN115463669A (en) * | 2022-09-13 | 2022-12-13 | 盐城工学院 | Multifunctional few-layer Ti 3 C 2 MXene/CdIn 2 S 4 Schottky type photocatalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170088429A1 (en) * | 2015-09-24 | 2017-03-30 | Samsung Electronics Co., Ltd. | Mxene nanosheet and manufacturing method thereof |
| CN107537540A (en) * | 2017-08-28 | 2018-01-05 | 浙江工业大学 | A kind of MXene (Ti3C2) loaded palladium catalyst and its preparation method and application |
| CN108455524A (en) * | 2018-01-18 | 2018-08-28 | 中国科学院理化技术研究所 | A kind of application of transition metal carbide |
| CN110548531A (en) * | 2019-09-06 | 2019-12-10 | 安徽工业大学 | method for dehydrogenating ammonia borane by using Ni-Pd catalyst through visible light catalysis |
-
2021
- 2021-06-11 CN CN202110652199.6A patent/CN113385206A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170088429A1 (en) * | 2015-09-24 | 2017-03-30 | Samsung Electronics Co., Ltd. | Mxene nanosheet and manufacturing method thereof |
| CN107537540A (en) * | 2017-08-28 | 2018-01-05 | 浙江工业大学 | A kind of MXene (Ti3C2) loaded palladium catalyst and its preparation method and application |
| CN108455524A (en) * | 2018-01-18 | 2018-08-28 | 中国科学院理化技术研究所 | A kind of application of transition metal carbide |
| CN110548531A (en) * | 2019-09-06 | 2019-12-10 | 安徽工业大学 | method for dehydrogenating ammonia borane by using Ni-Pd catalyst through visible light catalysis |
Non-Patent Citations (2)
| Title |
|---|
| GUANGYIN FAN ET AL.: "Palladium Supported on Titanium Carbide: A Highly Efficient, Durable, and Recyclable Bifunctional Catalyst for the Transformation of 4-Chlorophenol and 4-Nitrophenol" * |
| YALAN CHEN ET AL.: "Smart construction of oxidized-Ti3C2TX stabilized Rh nanoparticles for remarkable improving the catalytic performance for ammonia borane hydrolysis" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959344A (en) * | 2022-06-08 | 2022-08-30 | 郑州大学 | High-strength Ti 3 C 2 T x Magnesium alloy ZK61 and preparation method thereof |
| CN115463669A (en) * | 2022-09-13 | 2022-12-13 | 盐城工学院 | Multifunctional few-layer Ti 3 C 2 MXene/CdIn 2 S 4 Schottky type photocatalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111468167A (en) | Cobalt monoatomic supported nitrogen-doped carbon-oxygen reduction catalyst and preparation method thereof | |
| CN110743603B (en) | Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof | |
| CN110743596A (en) | Ruthenium nanoparticle/three-dimensional porous carbon nitride composite material, and preparation method and application thereof | |
| CN113529103B (en) | Method for preparing high-load transition metal monoatomic catalyst | |
| CN113385206A (en) | High-efficiency hydrogen production catalyst under strong interaction of metal carriers and preparation method | |
| CN113604838A (en) | Preparation method and application of nickel-cobalt bimetallic selenide heterostructure electrocatalyst | |
| CN110624550A (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| CN114685805B (en) | Preparation method for directly synthesizing MOF material for electrocatalytic carbon dioxide reduction at room temperature | |
| CN112725819A (en) | Tungsten-molybdenum-based nitrogen carbide nano material and preparation method and application thereof | |
| CN109174143B (en) | Perovskite-based composite nano photocatalytic material and preparation method and application thereof | |
| CN114284515B (en) | Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation method and application of composite material | |
| CN112958096B (en) | Preparation method and application of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth in sheet-shaped tri-titanium carbide composite photocatalyst | |
| CN113235108B (en) | MXene-loaded noble metal cluster catalyst and preparation method and application thereof | |
| CN112820886A (en) | Three-dimensional grading porous nonmetal carbon-based material and preparation method and application thereof | |
| CN112909271A (en) | Integral transition metal phosphide electrocatalyst with sea urchin-shaped morphology and preparation method and application thereof | |
| CN109267095B (en) | Novel nickel phosphide catalyst and preparation method thereof | |
| CN112717958B (en) | Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst | |
| CN111807336B (en) | Amorphous molybdenum oxide nanodot/two-dimensional carbon nitride nanosheet with photocatalysis and photothermal conversion performances and preparation method thereof | |
| CN114068952A (en) | Integral transition metal nitride electrocatalyst with flower-like structure and preparation method and application thereof | |
| CN113441186A (en) | Metal-organic framework-based ternary composite material and preparation method thereof | |
| CN108878897B (en) | One-dimensional nanowire cerium hydroxycarbonate/graphene composite material and preparation method thereof | |
| CN113522368A (en) | Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and preparation method thereof | |
| CN113258085A (en) | Oxygen-containing silicon nanosheet supported noble metal catalyst and preparation method and application thereof | |
| CN112390293A (en) | Ultrathin two-dimensional mangano-manganic oxide and two-dimensional Ni-Mn LDH nano composite material as well as preparation method and application thereof | |
| CN111359637A (en) | Hydrogen production catalyst nickel diselenide nanoparticle @ carbon nanosheet composite material and preparation method and application thereof |
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 |