CN109433261B - Preparation method of Ru/C nano assembly - Google Patents

Preparation method of Ru/C nano assembly Download PDF

Info

Publication number
CN109433261B
CN109433261B CN201811444954.6A CN201811444954A CN109433261B CN 109433261 B CN109433261 B CN 109433261B CN 201811444954 A CN201811444954 A CN 201811444954A CN 109433261 B CN109433261 B CN 109433261B
Authority
CN
China
Prior art keywords
nano
assembly
solution
prepared
temperature
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.)
Active
Application number
CN201811444954.6A
Other languages
Chinese (zh)
Other versions
CN109433261A (en
Inventor
徐平
李昱芝
张彬
杜耘辰
韩喜江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201811444954.6A priority Critical patent/CN109433261B/en
Publication of CN109433261A publication Critical patent/CN109433261A/en
Application granted granted Critical
Publication of CN109433261B publication Critical patent/CN109433261B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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 preparation method of a Ru/C nano assembly, and relates to the field of preparation methods of noble metal modified carbon nano composite materials. The invention aims to solve the technical problems of low catalytic efficiency, low reserves and high cost of the existing catalyst for electrochemical reaction. The method comprises the following steps: RuCl is synthesized by a mode of synthesizing Ru-MOF with a KUST-1-like structure3·xH2Mixing O, 1,3, 5-trimesic acid, acetic acid, ethanol and water, and carrying out hydrothermal reaction at high temperature to directly obtain the Ru/C nano assembly with a sponge-like structure in one step. The catalyst has good catalytic activity on the precipitation and oxidation of hydrogen. The invention is used for preparing the Ru/C nano assembly, and the prepared material is used for hydrogen evolution by water electrolysis and anode hydrogen oxidation reaction of a fuel cell.

Description

Preparation method of Ru/C nano assembly
Technical Field
The invention relates to the field of preparation methods of noble metal modified carbon nano composite materials.
Background
In the modern society, the development of human beings is closely related to energy. For more than two centuries, human energy supply has relied primarily on non-renewable fossil fuels such as petroleum and natural gas. However, with the increasing exhaustion of oil, coal and other energy sources and the environmental problems caused by the combustion of fossil fuels, such as global warming, air and water pollution, the search for a new green recyclable energy source is urgent. Among various energy sources, hydrogen can be produced independently, and the hydrogen-rich fuel has the advantages of high combustion heat value, no pollution in combustion, rich raw materials, convenience in storage and transportation and the like, and is a clean energy source with high competitiveness. Among various hydrogen production methods, the hydrogen production by electrolyzing water has abundant raw materials, and the recyclability of hydrogen production and utilization becomes the most ideal hydrogen production method at present. The preparation of the high-efficiency catalyst has important significance for hydrogen evolution of electrolyzed water and reverse reaction thereof by improving the hydrogen evolution reaction efficiency and reducing the overpotential of the reaction. However, the slow kinetic reaction severely limits the efficiency of the whole energy conversion device due to the large number of steps in the proton-coupled electron transfer process. Today, noble platinum-based metal materials are the most efficient catalysts, but their high cost and low inventory limit their large-scale use. Therefore, designing and synthesizing a low-platinum or non-platinum catalyst in the field of electrocatalysis is a new breakthrough for the field of electrocatalysis.
Disclosure of Invention
The invention provides a preparation method of a Ru/C nano assembly, aiming at solving the technical problems of low catalytic efficiency, low reserve and high cost of the existing catalyst for electrochemical reaction.
A preparation method of a Ru/C nano assembly is carried out according to the following steps:
firstly, RuCl3·xH2Dissolving O in acetic acid water solution, magnetically stirring to obtain uniform brown solution A,
dissolving 1,3, 5-trimesic acid in absolute ethyl alcohol, and magnetically stirring to obtain a clear and transparent solution B;
pouring the solution B obtained in the step two into the solution A obtained in the step one, uniformly stirring by magnetic force, transferring to a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling the product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
fourthly, washing the solid matter obtained in the third step for multiple times by adopting deionized water and ethanol, and then drying to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-H2O/CH3CH2OH。
A preparation method of a Ru/C nano assembly is carried out according to the following steps:
firstly, RuCl3·xH2Adding O and 1,3, 5-trimesic acid into an acetic acid aqueous solution, and magnetically stirring to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid substance obtained in the second step for many times by using deionized water and ethanol, then drying,obtaining the Ru/C nano assembly with a spongy structure and a chemical formula of Ru/C-H2O。
A preparation method of a Ru/C nano assembly is carried out according to the following steps:
firstly, RuCl3·xH2Adding O and 1,3, 5-trimesic acid into an absolute ethyl alcohol solution of acetic acid, and magnetically stirring to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid matter obtained in the second step for multiple times by using deionized water and ethanol, and then drying to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-CH3CH2OH。
The invention has the beneficial effects that:
the invention uses RuCl3·xH2The catalyst is a Ru/C nano assembly catalyst which is of a sponge-like structure and is formed by self-assembly of Ru nano particles loaded on carbon with the particle size of about 4nm in a water-alcohol mixed system through a one-step high-temperature hydrothermal method, wherein O is used as a ruthenium source, 1,3, 5-trimesic acid is used as an organic chain, acetic acid is used as a stabilizer.
The Ru/C nano assembly obtained by the invention has a spongy loose structure, so that a large number of active sites of the catalyst are exposed, and the mass transfer and charge transfer capacity of the catalyst in the catalysis process is accelerated. Particularly, when the Ru/C nano assembled sphere prepared in an alcohol-water mixed system is used as a catalyst for Hydrogen Evolution (HER) by water electrolysis, the catalytic activity similar to that of commercial platinum carbon is shown, and the current density is 10mA/cm2In the process, the overpotential is only 35mV, and the current is almost kept constant through a long-time stability test under constant voltage, so that excellent catalytic stability is shown. Meanwhile, when the composite material is used as an anode of a hydrogen fuel cell to perform Hydrogen Oxidation (HOR) reaction, the mass activity and the exchange current density of the composite material are also comparable to those of commercial Pt/C.
Although the material also belongs to a noble metal platinum element, the price of the material is only 1/10 of the noble metal platinum, the material is used for hydrogen production and hydrogen oxidation by electrolyzing water, the electrocatalytic activity which is comparable to that of commercial Pt/C is shown, the reaction cost is reduced, and a new idea is provided for preparing a catalyst which is low in cost, high in catalytic activity and good in stability and is used for converting renewable energy sources.
The invention is used for preparing the Ru/C nano assembly, and the prepared material is used for hydrogen evolution by water electrolysis and anode hydrogen oxidation reaction of a fuel cell.
Drawings
FIG. 1 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly and Ru/C-CH prepared in example III3CH2XRD spectrogram of the OH nano assembly;
FIG. 2 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly and Ru/C-CH prepared in example III3CH2Raman spectrum of OH nanometer assembly;
FIG. 3 shows Ru/C-H obtained in example one2O/CH3CH2A full spectrum of XPS spectra of OH nano-assemblies;
FIG. 4 shows Ru/C-H obtained in the first example2O/CH3CH2An element peak separation diagram of the binding energy of the OH nano assembly body at 275-295 eV;
FIG. 5 shows Ru/C-H obtained in the first example2O/CH3CH2An element peak separation diagram of OH nanometer assembly binding energy of 450-510 eV;
FIG. 6 shows Ru/C-H prepared in example one2O/CH3CH2Transmission Electron Microscopy (TEM) images of OH nano-assemblies,
FIG. 7 shows Ru/C-CH prepared in example two3CH2Transmission Electron Microscopy (TEM) images of OH nano-assemblies,
FIG. 8 shows Ru/C-H prepared in example III2Transmission Electron Microscopy (TEM) images of O nano-assemblies,
FIG. 9 shows Ru/C-H prepared in example one2O/CH3CH2Particle size distribution map of OH nano-assembly;
FIG. 10 shows Ru/C-H prepared in example one2O/CH3CH2HRTEM image of OH nano-assembly,
FIG. 11 shows Ru/C-H prepared in example one2O/CH3CH2SAED profile of OH nano-assemblies;
FIG. 12 example one Ru/C-H prepared2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly and Ru/C-CH prepared in example III3CH2Thermogravimetric (TG) profile of OH nano-assembly, wherein a represents Ru/C-H2O, b represent Ru/C-H2O/CH3CH2OH, C represents Ru/C-CH3CH2OH；
FIG. 13 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Linear Scanning (LSV) profile (acidic) of OH nano-assemblies and commercial Pt/C and ruthenium powder;
FIG. 14 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Tafel slope plots (acidic) for OH nano-assemblies and commercial Pt/C and ruthenium powders;
FIG. 15 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Effective active area plots (acidic) for OH nano-assemblies and commercial Pt/C and ruthenium powders;
FIG. 16 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2AC impedance plots (acidic) for OH nano-assemblies and commercial Pt/C and ruthenium powders,
in FIGS. 13-16, □ represents Ru/C-H2O, ". smallcircle" stands for Ru/C-H2O/CH3CH2OH, ". DELTA" stands for Ru/C-CH3CH2OH, "it" represents ruthenium powder,
Figure GDA0002725581570000041
represents the Pt/C ratio of the carbon fiber,
FIG. 17 shows Ru/C-H prepared in example one2O/CH3CH2Comparing polarization curves of the OH nano assembly before and after 1000 cycles of electrocatalytic water splitting hydrogen production reaction in an acid electrolyte, wherein '□' represents 1 cycle of the cycle, and 'O' represents 1000 cycles of the cycle (acidity);
FIG. 18 shows Ru/C-H prepared in example one2O/CH3CH2The change curve graph of the current of the OH nano assembly along with the time under constant voltage (acidity);
FIG. 19 shows Ru/C-H after 1000 cycles of CV2O/CH3CH2TEM image (50nm) (acidic) of OH nano-assembly sample;
FIG. 20 shows Ru/C-H after 1000 cycles of CV2O/CH3CH2HRTEM (2nm) (acidic) of OH nano-assembly samples;
FIG. 21 Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Polarization profiles of OH nano-assemblies and commercial Pt/C and ruthenium powders in KOH solution at a concentration of 1 mol/L;
FIG. 22 Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Tafel slope plots (basic) for OH nano-assemblies and commercial Pt/C and ruthenium powders;
FIG. 23 shows Ru/C-H prepared in example one2O/CH3CH2OH nano-groupPackage, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2HER polarization plots of OH nano-assemblies and commercial Pt/C and ruthenium powder in neutral electrolyte;
FIG. 24 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Tafel slope plots (neutral) for OH nano-assemblies and commercial Pt/C and ruthenium powders;
in FIGS. 21-24, □ represents Ru/C-H2O, ". smallcircle" stands for Ru/C-H2O/CH3CH2OH, ". DELTA" stands for Ru/C-CH3CH2OH, "it" represents ruthenium powder,
Figure GDA0002725581570000042
represents Pt/C;
FIG. 25 shows Ru/C-H prepared in example one2O/CH3CH2The OH nano assembly is subjected to a polarization curve diagram before and after 1000 CV cycles of reaction for preparing hydrogen by electrocatalytic decomposition of water in alkaline electrolyte, wherein '□' represents 1 cycle of the reaction, and 'O' represents 1000 cycles of the reaction;
FIG. 26 shows Ru/C-H prepared in example one2O/CH3CH2The OH nano assembly is subjected to a polarization curve diagram before and after 1000 CV cycles of reaction for preparing hydrogen by electrocatalytic decomposition of water in neutral electrolyte, wherein '□' represents 1 cycle of the reaction, and 'O' represents 1000 cycles of the reaction;
FIG. 27 shows Ru/C-H prepared in example one2O/CH3CH2TEM image of reaction circulation 1000 CV of hydrogen production by electrocatalytic decomposition of water of OH nano assembly in alkaline electrolyte,
FIG. 28 shows Ru/C-H prepared in example one2O/CH3CH2TEM image of reaction circulation 1000 CV of OH nano assembly in neutral electrolyte for hydrogen production by electrocatalytic decomposition of water,
FIG. 29 shows Ru/C-H prepared in example one2O/CH3CH2The Raman spectrogram of the catalyst after the OH nano assembly circulates for 1000 cycles of CV in acidic, alkaline and neutral electrolytes;
FIG. 30 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Comparative plots of polarization curves for OH nano-assemblies and commercial Pt/C and ruthenium powders in 0.1mol/L KOH solution,
FIG. 31 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Tafel plot of OH nano-assemblies and commercial Pt/C and ruthenium powders in 0.1mol/L KOH solution,
in FIGS. 30 to 31, □ represents Ru/C-H2O, ". smallcircle" stands for Ru/C-H2O/CH3CH2OH, ". DELTA" stands for Ru/C-CH3CH2OH, "it" represents ruthenium powder,
Figure GDA0002725581570000051
represents Pt/C;
FIG. 32 shows Ru/C-H at a sweep rate of 1mV/s2O/CH3CH2The polarization curves (basic) of OH at different rotation speeds, "□" for 400rpm, ". smallcircle" for 900rpm, ". DELTA" for 1600rpm, ". four-star" for 2500rpm,
Figure GDA0002725581570000052
represents 3600 rpm;
FIG. 33 shows Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Comparison of mass activity and exchange current density (basic) for OH nano-assemblies and commercial Pt/C and ruthenium powder; wherein
Figure GDA0002725581570000053
Representing mass activityThe nature of the Chinese herbal medicine is that,
Figure GDA0002725581570000054
represents the exchange current density;
FIG. 34 shows Ru/C-H prepared in example one2O/CH3CH2Polarization curves of OH nano-assemblies subjected to electrocatalytic hydrogen oxidation in alkaline electrolyte before and after 1000 cycles are compared, wherein '□' represents cycle 1 cycle, and 'O' represents cycle 1000 cycles;
FIG. 35 shows Ru/C-H prepared in example one2O/CH3CH2A change curve graph of current of the OH nano assembly along with time under constant voltage in alkaline electrolyte;
FIG. 36 shows Ru/C-H after 1000 cycles of CV2O/CH3CH2TEM image (50nm) (basic) of OH nano-assembly sample;
FIG. 37 shows Ru/C-H after 1000 cycles of CV cycling2O/CH3CH2HRTEM (2nm) (basic) of OH nano-assembly samples;
FIG. 38 shows Ru/C-H obtained in first verification experiment2O/CH3CH2TEM image of OH-1 assemblies;
FIG. 39 shows Ru-H prepared in verification experiment two2O/CH3CH2TEM image of OH-2 assemblies;
FIG. 40 verification of Ru-H from experiment three2O/CH3CH2TEM image of OH-3 assemblies;
FIG. 41 verifies the Ru-H from experiment four2TEM image of O-1 assembly;
FIG. 42 shows the Ru-CH obtained in experiment five3CH2TEM image of OH-1 assemblies;
FIG. 43 is an XRD spectrum of a catalyst prepared by a validation experiment;
FIG. 44 shows Ru-H obtained in validation experiment two2O/CH3CH2Raman spectrum of OH-2 catalyst.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the Ru/C nano assembly of the embodiment comprises the following steps:
firstly, RuCl3·xH2Dissolving O in acetic acid water solution, magnetically stirring to obtain uniform brown solution A,
dissolving 1,3, 5-trimesic acid in absolute ethyl alcohol, and magnetically stirring to obtain a clear and transparent solution B;
pouring the solution B obtained in the step two into the solution A obtained in the step one, uniformly stirring by magnetic force, transferring to a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling the product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
fourthly, washing the solid matter obtained in the third step for multiple times by adopting deionized water and ethanol, and then drying to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-H2O/CH3CH2OH。
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: RuCl in step one3·xH2The concentration of O is 0.1-0.5 mol/L. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: RuCl in step one3·xH2The concentration of O was 0.357 mol/L. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the first step, the concentration of the acetic acid aqueous solution is 0.05-0.6 mol/L. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and the concentration of the 1,3, 5-trimesic acid in the solution B in the second step is 0.02-0.3 mol/L. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the volume ratio of the deionized water in the acetic acid aqueous solution in the first step to the absolute ethyl alcohol in the second step is 1: 1. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the magnetic stirring time in the third step is 20 min. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: in the fourth step, the drying temperature is 60 ℃, and the vacuum drying is carried out for 12 hours. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the preparation method of the Ru/C nano assembly of the embodiment comprises the following steps:
firstly, RuCl3·xH2Adding O and 1,3, 5-trimesic acid into an acetic acid aqueous solution, and magnetically stirring to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid matter obtained in the second step for multiple times by using deionized water and ethanol, and then drying to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-H2O。
The detailed implementation mode is ten: the preparation method of the Ru/C nano assembly of the embodiment comprises the following steps:
firstly, RuCl3·xH2Adding O and 1,3, 5-trimesic acid into an absolute ethyl alcohol solution of acetic acid, and magnetically stirring to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, adopting deionized water and ethanol for multiple cleaning stepsSecondly, drying the obtained solid substance to obtain the Ru/C nano assembly with the sponge structure, wherein the chemical formula is Ru/C-CH3CH2OH。
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the preparation method of the Ru/C nano-assembly of the present embodiment is performed according to the following steps:
firstly, 0.6225g of RuCl3·xH2Dissolving O in 8.4mL of 0.595mol/L acetic acid aqueous solution, magnetically stirring to obtain uniform brown solution A,
secondly, dissolving 0.42g of 1,3, 5-trimesic acid in 8.4mL of absolute ethanol, and uniformly stirring by magnetic force to obtain a clear and transparent solution B;
thirdly, pouring the solution B obtained in the second step into the solution A obtained in the first step, magnetically stirring for 20min, then transferring to a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160 ℃, keeping the temperature for 72h, naturally cooling the product to room temperature after the reaction is finished, and centrifugally separating to obtain a solid substance;
fourthly, washing the solid matter obtained in the third step for multiple times by using deionized water and ethanol, and then drying at the temperature of 60 ℃ for 12 hours to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-H2O/CH3CH2OH。
Example two:
the preparation method of the Ru/C nano-assembly of the present embodiment is performed according to the following steps:
firstly, 0.6225g of RuCl3·xH2Adding O and 0.42g of 1,3, 5-trimesic acid into 16.8mL of 0.298mol/L acetic acid aqueous solution, and magnetically stirring for 20min to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160 ℃, keeping the temperature for 72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the mixture for multiple times by using deionized water and ethanolDrying the solid matter at 60 deg.C for 12 hr to obtain a Ru/C nano assembly with sponge structure and Ru/C-H chemical formula2O。
Example three:
the preparation method of the Ru/C nano-assembly of the present embodiment is performed according to the following steps:
firstly, 0.6225g of RuCl3·xH2Adding O and 0.42g of 1,3, 5-trimesic acid into 16.8mL of absolute ethanol solution of acetic acid with the concentration of 0.298mol/L, and magnetically stirring for 20min to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160 ℃, keeping the temperature for 72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid matter obtained in the second step for multiple times by using deionized water and ethanol, and then drying at 60 ℃ for 12 hours in vacuum to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-CH3CH2OH。
Example four:
the preparation method of the Ru/C nano-assembly of the present embodiment is performed according to the following steps:
firstly, 0.2mol/L RuCl3·xH2Dispersing O in 8.4mL of deionized water containing 0.4mol/L of acetic acid, and magnetically stirring to obtain a uniform brown solution A;
secondly, mixing 0.1 mol/L1, 3, 5-trimesic acid (H)3BTC) is dissolved in 8.4mL of absolute ethyl alcohol, and the solution is stirred uniformly by magnetic force to obtain clear and transparent solution B;
thirdly, pouring the solution B obtained in the second step into the solution A obtained in the first step, magnetically stirring for 20min, then transferring to a polytetrafluoroethylene reaction kettle, controlling the temperature to be 170 ℃, keeping the temperature for 48h, naturally cooling the product to room temperature after the reaction is finished, and centrifugally separating to obtain a solid substance;
fourthly, washing the solid matter obtained in the third step for multiple times by using deionized water and ethanol, and then drying the solid matterThe processing temperature is 60 ℃, the vacuum drying time is 12H, and the Ru/C nano assembly with the spongy structure is obtained, and the chemical formula is Ru/C-H2O/CH3CH2OH。
Ru/C-H obtained in this example2O/CH3CH2The OH catalyst is applied to the reaction of hydrogen production by electrocatalytic decomposition of water, and the current density of the OH catalyst is 10mA/cm2The overpotential was only 40 mV.
EXAMPLE one preparation of Ru/C-H2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly and Ru/C-CH prepared in example III3CH2The XRD spectrum of the OH nano-assembly is shown in figure 1, and it can be seen that the crystal form of the Ru nano-particle is cubic, corresponding to PDF card 06-0663, wherein the peaks at 2 theta of 38.3,42.1,44.0,58.3,69.4,78.3,82.2,84.7 degrees and 85.9 degrees correspond to the (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal faces of the Ru nano-particle respectively. Shows that under the action of high temperature and high pressure, Ru is successfully reacted in different reaction systems3+Reducing the solution into Ru simple substance nano particles.
EXAMPLE one preparation of Ru/C-H2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly and Ru/C-CH prepared in example III3CH2The Raman spectrum of the OH nano-assembly is shown in figure 2, and it can be seen from the figure that three samples are in 1360cm-1And-1586 cm-1Two peaks appear, corresponding to the D and G bands of graphitic carbon, respectively. Although the nano-assembly formed by the one-step hydrothermal process contains carbon, the crystallinity of the carbon formed by this method is poor.
For further analysis of the form of the sample, example one obtains Ru/C-H2O/CH3CH2The full spectrum of an XPS spectrum of the OH nano assembly is shown in figure 3, the element peak separation diagram of the binding energy of 275-295 eV is shown in figure 4, the element peak separation diagram of the binding energy of 450-510 eV is shown in figure 5, and the substance contains three elements of Ru, O and C as can be seen from the full spectrum. As can be seen from FIG. 4, the spectrum of Ru 3d + C1s3 peaks can be separated, wherein 281.3eV corresponds to Ru 3d of Ru simple substance5/2285eV Ru 3d attributable to the Ru simple substance3/2This peak coincides with C1s for C, and therefore, the peak is difficult to be accurately analyzed. FIG. 5 shows the result of peak separation of Ru 3p, where Ru 3p1/2And Ru 3p3/2The binding energies of the nanoparticles are 462.6eV and 484.9eV, respectively, and the results show that the Ru/C nanoparticles are composed of zero-valent elemental ruthenium and carbon, which is consistent with the results of XRD analysis.
EXAMPLE one preparation of Ru/C-H2O/CH3CH2A Transmission Electron Microscope (TEM) image of the OH nano-assembly is shown in FIG. 6, Ru/C-H prepared in example two2A Transmission Electron Microscope (TEM) image of the O nano-assembly is shown in FIG. 7, and Ru/C-CH prepared in example III3CH2A Transmission Electron Microscope (TEM) image of the OH nano-assembly is shown in FIG. 8, Ru/C-H prepared in example one2O/CH3CH2The distribution of the particle size of the OH nano-assembly is shown in fig. 9, and it can be seen from fig. 6 that the prepared product is not a single crystal structure formed by independent growth, but is a self-assembly, and is a secondary structure formed by self-assembly of small Ru nano-particles loaded on carbon. The nano-assembly presents a sponge-like structure, and has single dispersion and uniform particle size, and the particle size of each assembly is about 20-50 nm. From the particle size distribution chart of FIG. 9, it was found that the average size of Ru/C nanoparticles was 4 nm. As can be seen from FIGS. 8 and 9, when the reaction system is all-alcohol or all-water, the formed Ru/C nanocrystals are still spherical, and as can be seen from the edge of the sphere, the formed spherical Ru/C nanocrystals are also secondary structures formed by self-assembly of individual Ru/C nanoparticles. However, the assembled spheres formed in all-alcohol and all-water systems are more compact, no obvious pores are visible, and the particle size of the assembled spheres is larger and larger. The results show that the reaction system can influence the nucleation and growth of Ru/C nanocrystals.
EXAMPLE one preparation of Ru/C-H2O/CH3CH2HRTEM image of OH nano-assembly is shown in FIG. 10, Ru/C-H prepared in example one2O/CH3CH2OH nano-groupThe SAED pattern of the package is shown in fig. 11, and it can be seen from fig. 10 that the lattice spacing is 0.23 and 0.205nm, and in combination with fig. 11, the Ru nanoparticles prepared in the experiment have a hexagonal close-packed structure and excellent crystallinity, and the crystals grow along the (100) and (101) crystal planes.
EXAMPLE one preparation of Ru/C-H2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly and Ru/C-CH prepared in example III3CH2The Thermogravimetric (TG) plot of the OH nano-assembly is shown in FIG. 12, wherein a represents Ru/C-H2O, b represent Ru/C-H2O/CH3CH2OH, C represents Ru/C-CH3CH2OH; from the figure, it can be calculated that the contents of Ru are 91.44 wt%, 82.8 wt% and 90.6 wt%, respectively, and the result shows that the addition of anhydrous ethanol contributes to the dissolution of 1,3, 5-trimesic acid, thereby accelerating the generation of Ru nanoparticles.
EXAMPLE one preparation of Ru/C-H2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2Linear Scanning (LSV) curves of OH nano-assembly and commercial Pt/C and ruthenium powder are shown in FIG. 13, Tafel slope plot in FIG. 14, effective active area plot in FIG. 15, and AC impedance plot in FIG. 16, where "□" represents Ru/C-H2O, ". smallcircle" stands for Ru/C-H2O/CH3CH2OH, ". DELTA" stands for Ru/C-CH3CH2OH, "it" represents ruthenium powder,
Figure GDA0002725581570000101
representing Pt/C, Ru/C-H can be seen from FIGS. 13 and 142O/CH3CH2The OH nano-assembly catalyst has good catalytic performance and the current density is 10mA/cm2When the overpotential was only 35mV, the slope was 36.2mV/dec, which was smaller than the slope of the remaining samples and was close to Pt/C, indicating that Ru/C-H2O/CH3CH2OH at a current density of 10mA/cm2At about the same time, the current density increased most rapidly with the rise in overvoltage, indicating that Ru/C-H2O/CH3CH2OH has a faster kinetic process than other catalysts in the catalytic electrolysis of water to produce hydrogen. And the Tafel slope has a value between 30 and 120mV/dec, indicating a value of Ru/C-H2O/CH3CH2The hydrogen evolution reaction on the OH surface follows the Volmer-Tafel mechanism, and the electrochemical resolution process is the rate-limiting step of the reaction. As can be seen from FIG. 15, Ru/C-H2O/CH3CH2The electrochemically active area of OH is 3.52mF/cm2Greater than Ru/C-H2O(1.85mF/cm2)，Ru/C-CH3CH2OH(1.95mF/cm2) And Ru powder (0.08 mF/cm)2) Description of Ru/C-H2O/CH3CH2OH has more active sites at the solid-liquid interface, which may also be determined by its porous structure. As can be seen from FIG. 16, Ru/C-H was contained in all the catalysts2O/CH3CH2OH has the smallest charge transfer resistance, so the driving voltage required for charge transfer of the material is small, namely Ru/C-H2O/CH3CH2OH sponge-like spheres have the lowest voltage consumption, which is also Ru/C-H2O/CH3CH2One reason for HER performance of OH sponge spheres is optimal.
FIG. 17 shows Ru/C-H prepared in example one2O/CH3CH2The OH nano assembly is subjected to a polarization curve chart before and after 1000 cycles of electrocatalytic hydrogen production reaction by water decomposition in an acid electrolyte, wherein '□' represents 1 cycle of the cycle, and 'O' represents 1000 cycles of the cycle, and the acid electrolyte is H with the concentration of 0.5mol/L2SO4Solution, fig. 18 is a graph of current versus time at constant voltage, from which it can be seen that the HER catalytic performance of the material varies little.
Ru/C-H after 1000 cycles of CV2O/CH3CH2TEM image (50nm) of OH nanoassembly sample Ru/C-H after 1000 cycles of CV as shown in FIG. 192O/CH3CH2HRTEM image (2nm) of OH nano-assembly sample is shown in FIG. 20, and it can be seen from TEM and HRTEM image that the composition, size and morphology of the catalyst did not occur after long time testingA significant change. The information is combined to obtain the material with better HER catalytic stability in the acid electrolyte.
EXAMPLE one preparation of Ru/C-H2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2The polarization graphs of OH nano-assembly and commercial Pt/C and ruthenium powder in KOH solution with a concentration of 1mol/L are shown in FIG. 21, Tafel slope graph is shown in FIG. 22, the graph of HER performance test in neutral solution is shown in FIG. 23, and the Tafel slope graph is shown in FIG. 24, in which "□" represents Ru/C-H2O, ". smallcircle" stands for Ru/C-H2O/CH3CH2OH, ". DELTA" stands for Ru/C-CH3CH2OH, "it" represents ruthenium powder,
Figure GDA0002725581570000111
represents Pt/C, and Ru/C-H can be seen from the figure2O and Ru/C-CH3CH2OH phase ratio, Ru/C-H2O/CH3CH2OH likewise exhibits a lower overpotential at a current density of 10mA/cm2At this time, the overpotential was 53mV, but there was some gap in HER activity from commercial Pt/C. Similarly, FIGS. 23 and 24 show the HER performance of each catalyst in neutral solution, as can be seen from the LSV curves for each catalyst in the graphs, Ru/C-H2O/CH3CH2OH still exhibits far better performance than Ru/C-H2O and Ru/C-CH3CH2The hydrogen production performance of OH is remarkable in that Ru/C-H is in a neutral solution system2O/CH3CH2OH performance was even better than commercial Pt/C, indicating Ru/C-H2O/CH3CH2OH has great potential to replace commercial Pt/C as a high-efficiency hydrogen production catalyst and be applied to water electrolysis technology.
FIG. 25 shows Ru/C-H prepared in example one2O/CH3CH2The OH nano assembly is subjected to a polarization curve diagram before and after 1000 CV cycles of reaction for hydrogen production by electrocatalytic decomposition of water in alkaline electrolyte, and FIG. 26 is Ru/C-H prepared in the first embodiment2O/CH3CH2The polarization curve diagrams of the OH nano assembly before and after 1000 CV cycles of reaction for electrocatalytic water decomposition hydrogen production in neutral electrolyte are shown, wherein □ represents 1 cycle, and O represents 1000 cycles of cycle, and the catalyst also has good cycle stability in alkaline and neutral electrolytes.
FIG. 27 shows Ru/C-H prepared in example one2O/CH3CH2TEM image of OH nano-assembly after 1000 cycles of CV reaction for hydrogen production by electrocatalytic decomposition of water in alkaline electrolyte, wherein the alkaline electrolyte is KOH solution with a concentration of 1mol/L, and FIG. 28 is Ru/C-H prepared in the first example2O/CH3CH2TEM image of OH nano-assembly after 1000 cycles of CV reaction for hydrogen production by electrocatalytic decomposition of water in neutral electrolyte, and FIG. 29 is Ru/C-H prepared in the first example2O/CH3CH2And (3) circulating the OH nano assembly in acidic, alkaline and neutral electrolytes for 1000 cycles of CV to obtain a Raman spectrogram of the catalyst, wherein the alkaline electrolyte is a KOH solution with the concentration of 1mol/L, and the neutral electrolyte is a NaCl solution with the mass concentration of 3.5 wt%. As can be seen from fig. 27-29, the morphology of the catalyst did not change significantly in composition over a wide PH range over long periods of time. Further showing that the materials we synthesized have excellent stability.
Ru/C-H prepared in example one2O/CH3CH2OH Nano-Assembly, Ru/C-H prepared in example two2O nano-assembly, Ru/C-CH prepared in example III3CH2The OH nano-assembly and five samples of commercial Pt/C and ruthenium powder are applied to electrocatalytic hydrogen oxidation reaction, FIG. 30 is a comparison graph of polarization curves of each catalyst in 0.1M KOH solution, FIG. 31 is a corresponding Tafel plot, and "□" in FIGS. 30-31 represents Ru/C-H2O, ". smallcircle" stands for Ru/C-H2O/CH3CH2OH, ". DELTA" stands for Ru/C-CH3CH2OH, "it" represents ruthenium powder,
Figure GDA0002725581570000121
represents Pt/C;
FIG. 32 shows Ru/C-H at a sweep rate of 1mV/s2O/CH3CH2OH polarization curves at different rotational speeds, "□" represents 400rpm, "o" represents 900rpm, "Δ" represents 1600rpm, "fourstars represents 2500rpm,
Figure GDA0002725581570000122
represents 3600 rpm; FIG. 33 shows Ru/C-H prepared in this experiment2O/CH3CH2OH，Ru/C-H2O，Ru/C-CH3CH2Mass activity and exchange current density comparison of OH nano-assemblies and commercial Pt/C and ruthenium powders, wherein
Figure GDA0002725581570000123
Represents the activity of the compound in terms of mass,
Figure GDA0002725581570000124
represents the exchange current density; from the figure, Ru/C-H can be seen2O/CH3CH2The OH nano-assembly catalyst has good catalytic performance, and the mass activity reaches 37.6mA mg when the overpotential is 50mV-1The effective active area is 142.5mg cm-2Exhibit catalytic activity superior to commercial Pt/C.
FIG. 34 shows Ru/C-H prepared in example one2O/CH3CH2Comparison of polarization curves before and after 1000 cycles of electrocatalytic hydrogen oxidation reaction of OH nano-assembly in alkaline electrolyte, wherein "□" represents cycle 1, and ". smallcircle" represents cycle 1000, and FIG. 35 is a graph of current change with time under constant voltage, and it can be seen from the graph that the HOR catalytic performance of the material is little changed. Ru/C-H after 1000 cycles of CV2O/CH3CH2TEM image (50nm) of OH nanoassembly sample Ru/C-H after 1000 cycles of CV as shown in FIG. 362O/CH3CH2HRTEM image (2nm) of OH nano-assembly sample is shown in FIG. 37, and it can be seen from TEM and HRTEM image that the composition, size and morphology of the catalyst are not changed significantly after long time testing. Shows that the material has better HOR circulation in alkaline electrolyteAnd (4) stability.
As can be seen from the above characterization results, Ru/C-H having high electrocatalytic activity and low cost was successfully prepared using this example2O/CH3CH2An OH nano-assembly. The catalyst has excellent catalytic performance in the experimental application of electrocatalytic water decomposition hydrogen production and hydrogen oxidation.
In order to study the synthesis mechanism of the catalyst, the preparation method of the Ru nano-assembly of the present experiment was performed according to the following steps:
verification experiment I,
Firstly, 0.6225g of RuCl3·xH2Dissolving O in 8.4mL of aqueous solution, and magnetically stirring to obtain uniform brown solution A;
secondly, dissolving 0.42g of 1,3, 5-trimesic acid in 8.4mL of absolute ethanol, and magnetically stirring to obtain a clear and transparent solution B;
thirdly, pouring the solution B obtained in the second step into the solution A obtained in the first step, uniformly stirring by magnetic force, transferring the solution B into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160 ℃, keeping the temperature for 72 hours, naturally cooling the product to room temperature after the reaction is finished, and carrying out centrifugal separation to obtain a solid substance;
fourthly, washing the solid matter obtained in the third step for multiple times by using deionized water and ethanol, and then drying at the temperature of 60 ℃ for 12 hours to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-H2O/CH3CH2OH-1。
And (5) verifying an experiment II:
firstly, 0.6225g of RuCl3·xH2Dissolving O in 8.4mL of acetic acid aqueous solution with the concentration of 0.595mol/L, adding 8.4mL of absolute ethyl alcohol, and magnetically stirring for 20min to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160 ℃, keeping the temperature for 72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, the solid obtained in the second step is washed for a plurality of times by adopting deionized water and ethanolDrying at 60 deg.C for 12 hr to obtain product with chemical formula of Ru-H2O/CH3CH2OH-2。
And (3) a third verification experiment:
firstly, 0.6225g of RuCl3·xH2Dissolving O in a mixed solvent of 8.4mL of deionized water and 8.4mL of absolute ethyl alcohol, and magnetically stirring for 20min to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160 ℃, keeping the temperature for 72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid matter obtained in the second step for multiple times by using deionized water and ethanol, and then drying at 60 ℃ for 12 hours to obtain a product with a chemical formula of Ru-H2O/CH3CH2OH-3。
And (4) verifying an experiment:
firstly, 0.6225g of RuCl3·xH2Dispersing O in 16.8mL of deionized water, and magnetically stirring for 20min to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160 ℃, keeping the temperature for 72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid matter obtained in the second step for multiple times by using deionized water and ethanol, and then drying at 60 ℃ for 12 hours to obtain a product with a chemical formula of Ru-H2O-1。
And a fifth verification experiment:
firstly, 0.6225g of RuCl3·xH2Dispersing O in 16.8mL of absolute ethyl alcohol, and magnetically stirring for 20min to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160 ℃, keeping the temperature for 72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid matter obtained in the second step for multiple times by using deionized water and ethanol, and then drying at 60 ℃ for 12 hours to obtain a product with a chemical formula of Ru-CH3CH2OH-1。
Verify experiment one obtained black Ru/C-H2O/CH3CH2The TEM image of OH-1 is shown in FIG. 38, and it can be seen from FIG. 38 that when acetic acid is not added during the synthesis, the catalyst is formed by assembling small particles having substantially the same particle size, morphology and crystalline state, and the morphology of the assembled spheres is similar to that of the original spheres, but the size of the whole spheres is increased to about 50 nm. It is shown that the presence of acetic acid affects the growth rate of the particles, but does not affect the way the nanoparticles are assembled.
Verification experiment II prepared Ru-H2O/CH3CH2The low-power Transmission Electron Microscope (TEM) image of the OH-2 assembly is shown in FIG. 39, and it can be seen from the image that when 1,3, 5-trimesic acid is not added in the synthesis process, the formed catalyst is also spheres assembled by small particles with the particle size of about 4nm, the sphere size is not very uniform, the spheres are more compact than the original spheres, and the diameter of the spheres is further increased to about 50-100nm, which shows that the existence of 1,3, 5-trimesic acid can not only slow down the growth rate of the particles, but also improve the dispersibility thereof, prevent agglomeration among nano-particles in the growth process, increase the specific surface area of the product, provide more catalytic active sites, and thereby enhance the electrocatalytic activity.
Verification of Ru-H from experiment III2O/CH3CH2A TEM photograph of OH-3 is shown in FIG. 40, from which it can be seen that only RuCl is present during the synthesis3·xH2When O and water alcohol are mixed, the formed catalyst is also assembled by small particles with basically the same particle size, morphology and crystalline state, compared with the morphology obtained in the first and second tests, the degree of compactness of the sphere is further increased, and the diameter of the sphere is about 100-150 nm. The results show that Ru3+Independent of the presence of acetic acid and 1,3, 5-trimesic acid, but at a rate such that they grow on Ru nanoparticlesAnd the final assembly method.
Verification of Ru-H from experiment four2A TEM image of the O-1 assembled spheres is shown in FIG. 41, where it can be seen that only RuCl is present during the synthesis3·xH2And O and the aqueous solution, finally forming a sphere with a smooth surface, wherein the sphere is also assembled by small nanoparticles as seen from the edge of the sphere, but no gap exists between the particles, which indicates that the nanoparticles are adhered to each other in the growth process, grow together, agglomerate, and finally assemble into the sphere with the diameter of about 300-500 nm. Comparison of the morphology of the catalyst obtained in test three further shows that anhydrous ethanol is also not Ru3+The reason why the Ru is generated by reduction is also that the improvement effect of water on the dispersibility among the Ru nano particles is weaker.
Verification of the Ru-CH obtained in experiment five3CH2A TEM image of OH-1 assembled spheres is shown in FIG. 42, where it can be seen that only RuCl is present during the synthesis3·xH2The morphology of the finally formed catalyst was similar to that of the catalyst obtained in test one in O and ethanol solutions, indicating that water was also not Ru3+The reason why the Ru simple substance is generated by reduction is that the generation among Ru nano particles is accelerated by the existence of ethanol, and the dispersibility among the particles is improved.
Fig. 43 is an XRD spectrum diagram for verifying the experimentally prepared catalyst, and it can be seen from fig. 43 that the crystal form of the Ru nanoparticles is cubic, corresponding to PDF cards 06-0663, in which peaks at 38.3,42.1,44.0,58.3,69.4,78.3,82.2,84.7 ° and 85.9 ° 2 θ correspond to (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal planes of the Ru nanoparticles, respectively. This also further confirms that the formation of Ru nanoparticles stems from RuCl3·xH2O undergoes self-decomposition at high temperature and high pressure regardless of the kind of acid and reaction solvent.
FIG. 44 shows Ru-H obtained in validation experiment two2O/CH3CH2Raman spectrum of OH-2 catalyst, it can be seen from the figure that when 1,3, 5-trimesic acid was not added to the reaction mixture, the catalyst obtained was found to be 1360 and 1580cm-1No peak is generated, and the Ru/C nano formed on the surface is obtainedThe carbon in the rice assembly is derived from 1,3, 5-trimesic acid.
Through the tests, the synthesis mechanism of the Ru/C nano particle assembly prepared by the one-step hydrothermal method is probably RuCl3·xH2O first undergoes self-decomposition at high temperature and high pressure to form ruthenium nanoparticle seeds, which then nucleate and self-assemble with the aid of acid and reaction solvent to form Ru/C nanoparticle assemblies with a sponge-like structure.

Claims (9)

1. A preparation method of a Ru/C nano assembly is characterized by comprising the following steps:
firstly, RuCl3·xH2Dissolving O in acetic acid water solution, magnetically stirring to obtain uniform brown solution A,
dissolving 1,3, 5-trimesic acid in absolute ethyl alcohol, and magnetically stirring to obtain a clear and transparent solution B;
pouring the solution B obtained in the step two into the solution A obtained in the step one, uniformly stirring by magnetic force, transferring to a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling the product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
fourthly, washing the solid matter obtained in the third step for multiple times by adopting deionized water and ethanol, and then drying to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-H2O/CH3CH2OH；
And the concentration of the 1,3, 5-trimesic acid in the solution B in the second step is 0.02-0.3 mol/L.
2. The method of claim 1, wherein the step one is RuCl3·xH2The concentration of O is 0.1-0.5 mol/L.
3. The method of claim 1, wherein the step one is RuCl3·xH2The concentration of O was 0.357 mol/L.
4. The method of claim 1, wherein the concentration of the acetic acid solution in the first step is 0.05-0.6 mol/L.
5. The method according to claim 1, wherein the volume ratio of the deionized water in the acetic acid solution in the first step to the absolute ethyl alcohol in the second step is 1: 1.
6. The method for preparing Ru/C nano-assembly according to claim 1, wherein the magnetic stirring time in the third step is 20 min.
7. The method for preparing Ru/C nano-assembly according to claim 1, wherein the drying temperature in the fourth step is 60 ℃, and the drying time is 12h in vacuum.
8. A preparation method of a Ru/C nano assembly is characterized by comprising the following steps:
firstly, RuCl3·xH2Adding O and 1,3, 5-trimesic acid into an acetic acid aqueous solution, and magnetically stirring to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid matter obtained in the second step for multiple times by using deionized water and ethanol, and then drying to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-H2O。
9. A preparation method of a Ru/C nano assembly is characterized by comprising the following steps:
firstly, RuCl3·xH2Adding O and 1,3, 5-trimesic acid into anhydrous ethanol of acetic acidIn the solution, magnetically stirring to obtain a mixed solution;
secondly, transferring the mixed solution obtained in the first step into a polytetrafluoroethylene reaction kettle, controlling the temperature to be 160-180 ℃, keeping the temperature for 24-72 hours, naturally cooling a product to room temperature after the reaction is finished, and performing centrifugal separation to obtain a solid substance;
thirdly, washing the solid matter obtained in the second step by using deionized water and ethanol, and then drying to obtain the Ru/C nano assembly with the spongy structure, wherein the chemical formula is Ru/C-CH3CH2OH。
CN201811444954.6A 2018-11-29 2018-11-29 Preparation method of Ru/C nano assembly Active CN109433261B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811444954.6A CN109433261B (en) 2018-11-29 2018-11-29 Preparation method of Ru/C nano assembly

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811444954.6A CN109433261B (en) 2018-11-29 2018-11-29 Preparation method of Ru/C nano assembly

Publications (2)

Publication Number Publication Date
CN109433261A CN109433261A (en) 2019-03-08
CN109433261B true CN109433261B (en) 2021-01-29

Family

ID=65555932

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811444954.6A Active CN109433261B (en) 2018-11-29 2018-11-29 Preparation method of Ru/C nano assembly

Country Status (1)

Country Link
CN (1) CN109433261B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113584513A (en) * 2021-07-08 2021-11-02 南京信息工程大学 Method for preparing RuNC-T composite nano material and application thereof
CN114976075A (en) * 2022-06-06 2022-08-30 济南大学 Method for preparing ruthenium hollow colloidal sphere oxyhydrogen electrocatalyst by one-pot method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9474997B1 (en) * 2014-03-21 2016-10-25 The United States Of America As Represented By The Secretary Of The Army Metal-organic framework sorbents having hierarchical pore structure and method of making the same
CN105289733B (en) * 2015-10-28 2017-07-11 西南大学 Preparation method based on metal organic framework compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent
CN106824189B (en) * 2017-01-18 2019-04-26 中国科学技术大学 A kind of preparation method and its usage of ruthenium-molybdenum dioxide nano junction
CN108102108B (en) * 2017-12-25 2020-09-15 三峡大学 Preparation method of copper-based metal organic framework material and application of copper-based metal organic framework material in electro-catalysis hydrogen production
CN108842167B (en) * 2018-06-20 2020-05-12 中国石油大学(华东) Preparation method and application of coral-like NiSe @ NC

Also Published As

Publication number Publication date
CN109433261A (en) 2019-03-08

Similar Documents

Publication Publication Date Title
Yang et al. Iron-doped nickel disulfide nanoarray: A highly efficient and stable electrocatalyst for water splitting
Li et al. Nitrogen-doped Fe2O3/NiTe2 as an excellent bifunctional electrocatalyst for overall water splitting
Xue et al. Recent progress of Ni–Fe layered double hydroxide and beyond towards electrochemical water splitting
Wei et al. Honeycombed-like nanosheet array composite NiCo2O4/rGO for efficient methanol electrooxidation and supercapacitors
Cao et al. Improved hydrogen generation via a urea-assisted method over 3D hierarchical NiMo-based composite microrod arrays
Wang et al. Intercalation and elimination of carbonate ions of NiCo layered double hydroxide for enhanced oxygen evolution catalysis
Yang et al. A facile and scalable complexation-precipitation method of iron doped nickel hydroxide nanosheets as a superior oxygen evolution catalyst
CN113026032B (en) Ruthenium atom-level loaded manganese oxide catalyst and preparation method and application thereof
CN113265677B (en) Method for controllably synthesizing different crystal face preferred orientation Bi nanosheets
CN113258083B (en) Co X Bifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof
Kiran et al. Nickel-based nitrodopamine MOF and its derived composites functionalized with multi-walled carbon nanotubes for efficient OER applications
WO2022014377A1 (en) Catalyst, catalyst for water electrolysis cell, water electrolysis cell, water electrolysis device, and method for producing catalyst
CN112002915B (en) Oxygen electrode bifunctional catalyst, preparation method and application
Zhao et al. Hollow ZnxCo1-xSe2 microcubes derived from Metal–Organic framework as efficient bifunctional electrocatalysts for hydrogen evolution and oxygen evolution reactions
CN109433261B (en) Preparation method of Ru/C nano assembly
Zhang et al. Effect of the valence state of initial iron source on oxygen evolution activity of Fe-doped Ni-MOF
Wang et al. Two-dimensional PdSn/TiO2-GO towards ethanol electrooxidation catalyst with high stability
Li et al. Three-dimensional graphene-like carbon nanosheets coupled with MnCo-layered double hydroxides nanoflowers as efficient bifunctional oxygen electrocatalyst
Zhang et al. Amorphous mixed Ir–Mn oxide catalysts for the oxygen evolution reaction in PEM water electrolysis for H2 production
Silva et al. Green synthesis of CuCo2O4–CuO composite nanoparticles grown on nickel foam for high-performance oxygen evolution reaction
Hao et al. Nickel cobalt oxide nanowires with iron incorporation realizing a promising electrocatalytic oxygen evolution reaction
Lu et al. Coexisting Fe single atoms and nanoparticles on hierarchically porous carbon for high-efficiency oxygen reduction reaction and Zn-air batteries
Wu et al. Co-doped Pyrrhotite Fe7S8 nanosheets as bifunctional electrocatalysts for water splitting
Xie et al. Ultrasmall Co-NiP embedded into lantern shaped composite achieved by coordination confinement phosphorization for overall water splitting
Wu et al. Hierarchical core-shell structural Ni2P/NiMoO4@ CoP/FeP2 nanorods as difunctional electrocatalysts for efficient overall water splitting

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
GR01 Patent grant
GR01 Patent grant