CN117187872B - Preparation method and electrocatalytic application of silver-imidazole complex and Ag composite material - Google Patents
Preparation method and electrocatalytic application of silver-imidazole complex and Ag composite material Download PDFInfo
- Publication number
- CN117187872B CN117187872B CN202311461530.1A CN202311461530A CN117187872B CN 117187872 B CN117187872 B CN 117187872B CN 202311461530 A CN202311461530 A CN 202311461530A CN 117187872 B CN117187872 B CN 117187872B
- Authority
- CN
- China
- Prior art keywords
- silver
- solution
- imidazole
- composite material
- complex
- 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
Links
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 96
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000243 solution Substances 0.000 claims abstract description 49
- 229910052709 silver Inorganic materials 0.000 claims abstract description 38
- 239000004332 silver Substances 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 14
- 239000008149 soap solution Substances 0.000 claims description 13
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 12
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 12
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011365 complex material Substances 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 37
- 229910021642 ultra pure water Inorganic materials 0.000 abstract description 11
- 239000012498 ultrapure water Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 101710134784 Agnoprotein Proteins 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 238000002848 electrochemical method Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 238000001144 powder X-ray diffraction data Methods 0.000 description 10
- 230000005855 radiation Effects 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Abstract
The invention belongs to the technical field of material preparation, and particularly discloses a preparation method and electrocatalytic application of a silver-imidazole complex and Ag composite material. The method comprises the following steps: (1) cleaning silver flakes; (2) Weighing silver nitrate, dissolving in ammonia water, and adding ethanol to prepare solution A; pouring ethanol solution containing imidazole ligand into the solution A before electrolysis to obtain mixed solution B; (3) Connecting an electrochemical workstation, respectively placing the silver sheets treated in the anode and cathode clamps (1) into the mixed solution B; (4) And (3) performing electrochemical etching under a certain voltage, and washing the anode silver sheet in ultrapure water to obtain the composite material catalyst Ag-mim-a/Ag of the silver-imidazole complex and Ag. The silver-imidazole complex prepared by the invention has uniform crystal growth and high chemical stability, is not easy to oxidize in air, can be used for electrocatalytic CO2 reduction reaction, and has hydrogen Faraday efficiency of 16.2% and carbon monoxide Faraday efficiency of 76.5% under the optimal potential of-0.9V (vs.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a preparation method and electrocatalytic application of a silver-imidazole complex and Ag composite material.
Background
In recent years, a large amount of carbon dioxide (CO 2 ) The emission of gas has attracted attention both at home and abroad. Due to CO 2 Is detrimental to green sustainability development, so many new technologies are adopted to minimize CO 2 Is used for discharging or capturing CO in the atmosphere 2 Fixing. Can be used for converting CO in the atmosphere 2 Is converted into high-value chemical products and fuels. In the method of carbon dioxide conversion, the electrochemical reduction reaction system is green, modularized and easy to expand application. The power driving these processes may come from renewable energy sources such as solar and wind.
Wherein CO 2 Reduction to CO is CO 2 Reduction to multipleThe first step of the carbon product, and CO can be further synthesized into fuel, so CO 2 The conversion to CO is of great interest and has significant implications. On one hand, CO is in a gaseous state at normal temperature and normal pressure, and is extremely easy to separate under the electrocatalytic condition for later use; on the other hand, CO is an important chemical raw material, and is also a main raw material in synthesis gas. Silver has weak adsorption capacity to CO, CO is easily desorbed from the surface of the catalyst, and the product is mainly CO. However, the silver foil catalyst has a high overpotential, and the faraday efficiency of CO is low and the current utilization efficiency is low. Therefore, the preparation and synthesis technology of the modified material is the main research direction at present, and researchers try a plurality of methods to modify the silver foil so as to improve the electrocatalytic CO 2 The modified research of in-situ generation of metal organic framework composite catalyst by taking silver foil as substrate is less, the composite material is endowed with new characteristics of denser catalytic active center, larger specific surface area and the like by modification, and the catalyst has the effect of improving CO 2 Catalytic reduction reaction performance plays a critical role.
At present, the synthesis methods of the compounds are various and comprise a hydrothermal method, mechanical stirring, liquid diffusion and the like, but most of the methods have the problems of long time, high energy consumption, complex operation process and the like.
Disclosure of Invention
The invention aims at solving at least one of the technical problems in the prior art, and therefore, the invention provides a preparation method and electrocatalytic application of a silver-imidazole complex and Ag composite material, wherein the silver-imidazole complex and Ag composite material can be used for electrocatalytic CO 2 The material has the characteristics of uniform size, high selectivity and high stability in reduction reaction.
In order to achieve the above object, the preparation method of the present invention comprises the steps of:
(1) Cleaning silver flakes;
(2) Weighing silver nitrate, dissolving in ammonia water, and adding ethanol to obtain solution A; pouring ethanol solution containing imidazole ligand into the solution A before electrolysis to obtain mixed solution B;
(3) Connecting an electrochemical workstation, respectively clamping the silver sheets treated in the step (1) on the anode and cathode, and placing the silver sheets in the mixed solution B obtained in the step (2);
(4) And after electrochemical etching, washing the anode silver sheet to obtain a silver-imidazole complex and Ag composite material Ag-mim-a/Ag.
Ammonia is taken as a competing ligand, strong base and solvent, and cannot be replaced by other organic bases such as triethylamine and ethylenediamine; ethanol plays a role of a solvent in the process, and can be mutually dissolved with ammonia water and can dissolve methylimidazole ligand.
Further, the method for cleaning and treating silver flakes in the step (1) comprises the following steps: polishing silver flakes, and then sequentially cleaning the silver flakes in a soap solution, acetone, deionized water and ethanol by ultrasonic waves. Preferably, the ultrasonic cleaning is performed for 10 to 30 minutes.
Further, in the step (1), the thickness of the silver flake is 0.1-0.3mm, and the size of the silver flake is 0.25-4cm 2 。
Preferably, the thickness of the silver flake is 0.1mm, and the size of the silver flake is 0.25cm 2 Or 1cm 2 Or 2cm 2 Or 3cm 2 Or 4cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the silver flake is 0.3mm, and the size of the silver flake is 0.25cm 2 Or 1cm 2 Or 2cm 2 Or 3cm 2 Or 4cm 2 。
Further, the volume ratio of ammonia water to ethanol in the solution A is 1:10-50. Preferably, the volume ratio of ammonia to ethanol is 1:50, 1:25, 1:20, 1:15, 1:12.5 or 1:10.
Further, the imidazole ligand in the step (2) is at least one of 1-methylimidazole, 2-methylimidazole and 1, 2-dimethylimidazole.
Further, the concentration of the ethanol solution containing the imidazole ligand in the step (2) is 2-6 mg/mL.
Further, the molar ratio of the imidazole ligand to the silver nitrate is 2-6:1. Preferably, the molar ratio of the imidazole ligand to silver nitrate is 2:1, 4:1, 6:1, respectively.
Further, in the step (4), the electrochemical etching voltage is 3-7V #vs.Ag/AgCl)。
Further, in the step (4), the electrochemical etching time is 15-45 minutes.
The second object of the present invention is to provide a composite material Ag-mim-a/Ag of silver-imidazole complex and Ag obtained by the above preparation method, wherein Ag-mim-a is monoclinic, and the unit cell parameters are a= 7.8906 (7) a, b= 5.9706 (5) a, c= 10.8708 (9) a, β= 92.452 (1) °.
The third object of the present invention is to provide a use of the silver-imidazole complex material and Ag composite material, which can be used for electrocatalytic CO 2 And (3) reduction reaction.
The beneficial effects achieved by the invention are as follows:
the silver-imidazole complex is modified and synthesized on the surface of the metal foil by an electrosynthesis method, so that the problems of long time, high energy consumption, complex operation process and the like of the existing synthetic method can be well avoided. The synthesis process of the invention is green, and the thickness and the particle size of the surface complex can be regulated and controlled. The method for modifying the silver-imidazole complex directly synthesized on the surface of the silver foil can effectively reduce the contact between water and the metal foil and electrically catalyze CO 2 H for reducing competitive side reactions during reduction 2 The selectivity of CO products is enhanced, and the complex has Lewis acid sites, which is beneficial to CO adsorption 2 。
The silver-imidazole complex crystal prepared by the method has uniform growth on specific silver foil, high chemical stability, difficult oxidation in air, high electrocatalytic activity and good product selectivity. The silver foil and the silver-imidazole complex are compounded to form the silver-imidazole complex-Ag composite material, and the silver foil not only provides good conductivity to CO 2 The electrocatalytic reduction has a certain promotion effect, and can also play a good supporting role, so that the electrocatalytic reduction can be directly used as a working electrode for testing. Electrocatalytic CO 2 Reduction reaction at optimum potential of-0.9Vvs.RHE), the hydrogen faraday efficiency was 16.2% and the carbon monoxide faraday efficiency was 76.5%.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of Ag-mim-a in the silver-imidazole complex and Ag composite material prepared by the invention;
FIG. 2 is an X-ray diffraction pattern of a composite material of silver-imidazole complex and Ag prepared in examples 1-6 of the present invention;
FIG. 3 is an enlarged photograph of a composite material of Ag and silver-imidazole complex prepared in examples 1, 3, 4, 5, and 6 according to the present invention under an optical microscope;
FIG. 4 is an X-ray diffraction pattern of a composite material of silver-imidazole complex and Ag prepared in comparative examples 1-4 of the present invention;
FIG. 5 is an SEM image of a commercial silver foil (a) and a composite material (b) of silver-imidazole complex and Ag prepared in example 1 of the present invention;
FIG. 6 shows a composite of silver-imidazole complex and Ag prepared in examples 1 and 2 of the present invention with corresponding commercial silver foil catalyst at 0.1M KHCO 3 H in solution at different applied electrode potentials 2 And faraday efficiency of the CO product;
FIG. 7 shows a composite of silver-imidazole complex and Ag prepared in examples 1 and 2 of the present invention with corresponding commercial silver foil catalyst at 0.1M KHCO 3 Current density maps at different applied electrode potentials in solution;
FIG. 8 shows the silver-imidazole complex and Ag composite material prepared in example 1 of the present invention and pure complex Ag-mim-a at 0.1M KHCO 3 Current density maps at different applied electrode potentials in solution;
FIG. 9 shows a 0.1M KHCO composite of the silver-imidazole complex prepared in example 1 of the present invention and Ag 3 In solution, -0.9 and V%vs.RHE) stability test results graph;
FIG. 10 is a schematic diagram of a synthesis apparatus used in examples of the present invention and comparative examples.
Detailed Description
The invention and its embodiments are described below without limitation, and the actual embodiments are not limited thereto. In summary, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical solution should not be creatively devised without departing from the gist of the present invention.
Example 1
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
(1) Silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
(2) Weigh 0.05 g AgNO 3 Dissolving in 3 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.1 g of 2-methylimidazole and dissolving in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
(3) The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
(4) At 5V%vs.Ag/AgCl) is electrochemically etched for 30 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain the catalyst Ag-mim-a/01Ag.
The PXRD test is carried out by taking Ag-mim-a/01Ag, and the instrument used in the test process is a MiniFlex 600X-ray powder diffractometer of Rigaku company. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 2.
Taking an optical microscope photo of Ag-mim-a/01Ag, the magnification is 5.3, and the surface diagram of the catalyst is shown in FIG. 3.
Example 2
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.3mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. Silver flake is coated withUltrasonic cleaning is carried out in soap solution, acetone, deionized water and ethanol for 15 minutes to remove impurities adsorbed on the surface, and deionized water is used for thoroughly cleaning the silver flakes again. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 3 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.1 g of 2-methylimidazole and dissolving in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 30 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain the catalyst Ag-mim-a/03Ag.
The PXRD test is carried out by taking Ag-mim-a/03Ag, and the instrument used in the test process is a MiniFlex 600X-ray powder diffractometer of Rigaku company. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 2.
Example 3
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 3 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.1 g of 2-methylimidazole and dissolving in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 15 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain the catalyst Ag-mim-a/01Ag-15.
The PXRD test was performed on Ag-mim-a/01Ag-15, and the instrument used in the test was a MiniFlex 600X-ray powder diffractometer from Rigaku corporation. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 2.
Taking an optical microscope photo of Ag-mim-a/01Ag, the magnification is 5.3, and the surface diagram of the catalyst is shown in FIG. 3.
Example 4
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 3 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.1 g of 2-methylimidazole and dissolving in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 45 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain the catalyst Ag-mim-a/01Ag-45.
The PXRD test was performed on Ag-mim-a/01Ag-45, and the instrument used in the test was a MiniFlex 600X-ray powder diffractometer from Rigaku corporation. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 2.
Taking an optical microscope photo of Ag-mim-a/01Ag, the magnification is 5.3, and the surface diagram of the catalyst is shown in FIG. 3.
Example 5
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 3 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; 0.15 g of 2-methylimidazole is weighed and dissolved in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 30 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain a catalyst Ag-mim-a/01Ag-6:1.
The PXRD test was performed using an Ag-mim-a/01Ag-6:1, and the instrument used in the test was a MiniFlex 600X-ray powder diffractometer from Rigaku corporation. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 2.
Taking an optical microscope photo of Ag-mim-a/01Ag, the magnification is 5.3, and the surface diagram of the catalyst is shown in FIG. 3.
Example 6
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 3 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.05 g of 2-methylimidazole and dissolving in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 30 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain a catalyst Ag-mim-a/01Ag-2:1.
The PXRD test was performed using an Ag-mim-a/01Ag-2:1, and the instrument used in the test was a MiniFlex 600X-ray powder diffractometer from Rigaku corporation. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 2.
Taking an optical microscope photo of Ag-mim-a/01Ag, the magnification is 5.3, and the surface diagram of the catalyst is shown in FIG. 3.
Comparative example 1
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 1 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.1 g of 2-methylimidazole and dissolving in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 30 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain the catalyst Ag-mim-a/01Ag-1.
The PXRD test was performed on Ag-mim-a/01Ag-1, and the instrument used in the test was a MiniFlex 600X-ray powder diffractometer from Rigaku corporation. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 4.
Comparative example 2
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
the method comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 2 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.1 g of 2-methylImidazole is dissolved in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 30 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain the catalyst Ag-mim-a/01Ag-2.
The PXRD test was performed on Ag-mim-a/01Ag-2, and the instrument used in the test was a MiniFlex 600X-ray powder diffractometer from Rigaku corporation. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 4.
Comparative example 3
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 4 ml ammonia water, and then pouring 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.1 g of 2-methylimidazole and dissolving in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 30 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain the catalyst Ag-mim-a/01Ag-4.
The PXRD test was performed on Ag-mim-a/01Ag-4, and the instrument used in the test was a MiniFlex 600X-ray powder diffractometer from Rigaku corporation. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 4.
Comparative example 4
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 Dissolving in 5 ml ammonia water, and then pouring into 25 ml absolute ethyl alcohol to prepare a solution A; weighing 0.1 g of 2-methylimidazole and dissolving in 25 ml absolute ethyl alcohol to prepare a mixed solution; the mixed solution is poured into the solution A before electrolysis to obtain a mixed solution B.
The electrochemical workstation was connected using a three electrode system with the treated silver flakes on the cathode and anode clamps, respectively, and placed in the prepared solution B.
At 5V%vs.Ag/AgCl) is electrochemically etched for 30 minutes under the voltage, and the anode silver flake is washed in ultrapure water to obtain the catalyst Ag-mim-a/01Ag-5.
The PXRD test was performed on Ag-mim-a/01Ag-5, and the instrument used in the test was a MiniFlex 600X-ray powder diffractometer from Rigaku corporation. The PXRD pattern of the catalyst was measured using cukα (λ=1.5418 a) as the radiation source, at room temperature, with a scan range of 10-50 ° (2θ), a step size of 0.02 °, and a scan rate of 10 °/min, as shown in fig. 4.
Comparative example 5
A preparation method of a silver-imidazole complex and Ag composite material comprises the following steps:
silver flake purchased from reagent company and having a thickness of 0.1. 0.1mm was cut into 2cm 2 Small pieces of the size and polished smooth using 1000 mesh sandpaper. The silver flakes were sequentially ultrasonically cleaned in soap solution, acetone, deionized water and ethanol for 15 minutes to remove surface adsorbed impurities, and thoroughly cleaned again with deionized water. The silver flake which can be directly used for ligand etching electrochemical synthesis or electrochemical measurement is obtained.
Weigh 0.05 g AgNO 3 After pouring 25 ml absolute ethanol, 3 ml ammonia was added, leaving an insoluble white solid.
Comparative example 6
The procedure of example 1 was repeated except that the aqueous ammonia in step (2) was replaced with another organic base such as triethylamine and ethylenediamine, and the conditions and steps were the same as those of example 1, and the resultant mixture in step (2) had an insoluble white solid.
As can be seen from FIG. 1, the complex formed on the surface of the silver foil in example 1 is of the zigzag type;
as can be seen from fig. 2 and 3, in examples 1 to 6, diffraction peaks corresponding to the standard reference were observed, and a layer of substance was covered on the surface of the silver foil under a microscope; from examples 1 and 2, it is clear that 0.1mm silver foil is more favorable for the synthesis of the complex on the surface; from examples 1, 3, 4 it is clear that a deposition of 30 minutes is advantageous for a more uniform coverage of the surface complex; from examples 1, 5 and 6, it is shown that a molar ratio of 2-methylimidazole to silver nitrate of 4:1 is more advantageous for a uniform coverage of the complex.
As can be seen from FIG. 4, in each of comparative examples 1 to 4, although diffraction peaks corresponding to the standard reference were observed, the peak intensities were lower, and the effect was not as good as that of the use of 3 ml ammonia in the synthesis process of example 1.
As is clear from FIG. 5, the crystals of example 1 were excellent in dispersibility, regular in shape and uniform in size.
As can be seen from FIG. 6, the optimum potential in examples 1 and 2 is-0.9V%vs.RHE), the faraday efficiency of the CO product is effectively improved and the faraday efficiency of the hydrogen evolution reaction is effectively suppressed compared with the silver foil catalyst. The silver-imidazole complex and Ag composite material can be applied to electrocatalytic CO 2 In the reduction reaction, higher can be obtainedThe electrocatalytic activity and the selectivity thereof are better.
As can be seen from FIG. 7, the optimum potential in examples 1 and 2 was-0.9V [ ]vs.RHE), compared with silver foil catalyst, the current density is greatly improved, and the catalyst is used for CO 2 The reduction has better electrocatalytic performance.
As can be seen from fig. 8, the catalyst directly synthesized from example 1 has a lower overpotential and a higher current density at a low potential than the Ag-mim-a complex alone directly supported on the glassy carbon electrode.
As can be seen from fig. 9, the material prepared in example 1 was stable during the test period of 8 h, and the faraday efficiency of the CO product did not change much during electrolysis, indicating that the material prepared in example 1 had good stability.
As can be seen from fig. 10, the catalyst electrode obtained at the anode can be directly used for the subsequent electrochemical performance test using the treated silver foil as the cathode and anode placed in the configured B solution.
Claims (6)
1. The preparation method of the silver-imidazole complex and Ag composite material is characterized by comprising the following steps:
(1) Cleaning silver flakes;
(2) Weighing silver nitrate, dissolving in ammonia water, and adding ethanol to obtain solution A; pouring ethanol solution containing imidazole ligand into the solution A before electrolysis to obtain mixed solution B;
(3) Connecting an electrochemical workstation, respectively clamping the silver sheets treated in the step (1) on the anode and cathode, and placing the silver sheets in the mixed solution B obtained in the step (2);
(4) Washing the anode silver sheet after electrochemical etching to obtain a silver-imidazole complex and Ag composite material;
wherein the volume ratio of ammonia water to ethanol in the solution A in the step (2) is 1:10-50, the concentration of the ethanol solution containing imidazole ligand is 2-6 mg/mL, and the molar ratio of the imidazole ligand to the silver nitrate is 2-6:1; the imidazole ligand in the step (2) is at least one of 1-methylimidazole, 2-methylimidazole and 1, 2-dimethylimidazole;
the voltage of the electrochemical etching in the step (4) is 3-7V relative to Ag/AgCl.
2. The method of claim 1, wherein the step (1) of cleaning the silver flake comprises: polishing silver flakes, and then sequentially cleaning the silver flakes in a soap solution, acetone, deionized water and ethanol by ultrasonic waves.
3. The method according to claim 1, wherein the silver flake in step (1) has a thickness of 0.1 to 0.3mm and a silver flake size of 0.25 to 4cm 2 。
4. The method of claim 1, wherein the electrochemical etching time is 15-45 minutes.
5. A composite of silver-imidazole complex and Ag prepared by the preparation method according to any one of claims 1 to 4, wherein the composite of silver-imidazole complex and Ag is Ag-mim-a/Ag, the silver-imidazole complex Ag-mim-a is a zigzag, monoclinic system, the unit cell parameters are a= 7.8906 (7) a, b= 5.9706 (5) a, c= 10.8708 (9) a, β= 92.452 (1) °.
6. The silver-imidazole complex material and Ag composite material as claimed in claim 5 for electrocatalytic CO 2 Use in reduction reactions.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311461530.1A CN117187872B (en) | 2023-11-06 | 2023-11-06 | Preparation method and electrocatalytic application of silver-imidazole complex and Ag composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311461530.1A CN117187872B (en) | 2023-11-06 | 2023-11-06 | Preparation method and electrocatalytic application of silver-imidazole complex and Ag composite material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN117187872A CN117187872A (en) | 2023-12-08 |
CN117187872B true CN117187872B (en) | 2024-02-13 |
Family
ID=88994603
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311461530.1A Active CN117187872B (en) | 2023-11-06 | 2023-11-06 | Preparation method and electrocatalytic application of silver-imidazole complex and Ag composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117187872B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103665009A (en) * | 2013-11-22 | 2014-03-26 | 河南工程学院 | 1,4-di-(1-H-benzimidazolyl) butane-silver(I) complex and preparation method thereof |
CN112410804A (en) * | 2020-11-02 | 2021-02-26 | 浙江工业大学 | Silver-based catalyst for electrochemical reduction of carbon dioxide and preparation method thereof |
CN113555500A (en) * | 2021-06-25 | 2021-10-26 | 深圳大学 | Resistive random access memory and preparation method thereof |
-
2023
- 2023-11-06 CN CN202311461530.1A patent/CN117187872B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103665009A (en) * | 2013-11-22 | 2014-03-26 | 河南工程学院 | 1,4-di-(1-H-benzimidazolyl) butane-silver(I) complex and preparation method thereof |
CN112410804A (en) * | 2020-11-02 | 2021-02-26 | 浙江工业大学 | Silver-based catalyst for electrochemical reduction of carbon dioxide and preparation method thereof |
CN113555500A (en) * | 2021-06-25 | 2021-10-26 | 深圳大学 | Resistive random access memory and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
Electrodeposition of chitosan based on coordination with metal ions in situ-generated by electrochemical oxidation;zenghua geng等;J.Mater.Chem.B;第3331-3338页 * |
spectroscopic and electrochemical studies of reduction reactions for remediation and batteris;Andrew gewirth;ECS Meeting Abstracts;第1-3 * |
Also Published As
Publication number | Publication date |
---|---|
CN117187872A (en) | 2023-12-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Feng et al. | A bifunctional nanoporous Ni–Co–Se electrocatalyst with a superaerophobic surface for water and hydrazine oxidation | |
Khezri et al. | CO 2 reduction: the quest for electrocatalytic materials | |
Hua et al. | Pt nanoparticles supported on submicrometer-sized TiO2 spheres for effective methanol and ethanol oxidation | |
CN104549242B (en) | Preparation method of nanometer palladium-graphene three-dimensional porous composite electrocatalyst | |
CN110512228B (en) | Preparation method of nickel phosphide/nickel foam electrochemical functional hydrogen evolution material | |
CN107597169A (en) | A kind of multi-functional composite catalyst of biomass-based N doping porous carbon, preparation method and applications | |
Zhou et al. | In situ surface engineering of nickel inverse opal for enhanced overall electrocatalytic water splitting | |
CN113249739B (en) | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst | |
CN113136597B (en) | Copper-tin composite material and preparation method and application thereof | |
Jiang et al. | Porous and amorphous cobalt hydroxysulfide core–shell nanoneedles on Ti-mesh as a bifunctional electrocatalyst for energy-efficient hydrogen production via urea electrolysis | |
CN112981449B (en) | Ordered PEM water electrolysis membrane electrode anode catalyst layer and preparation method and application thereof | |
CN113279005A (en) | Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution | |
Lee et al. | Hierarchical cobalt oxide-functionalized silicon carbide nanowire array for efficient and robust oxygen evolution electro-catalysis | |
Yang et al. | Integrating electrocatalytic seawater splitting and biomass upgrading via bifunctional nickel cobalt phosphide nanorods | |
Zhang et al. | Few-atom-layer metallene quantum dots toward CO2 electroreduction at ampere-level current density and Zn-CO2 battery | |
Chen et al. | Gas penetrating hollow fiber Bi with contractive bond enables industry-level CO2 electroreduction | |
CN108315759A (en) | A kind of Cu of vanadium modification2S self-supportings electrode material and its synthetic method | |
Shixuan et al. | Oxygen reduction activity of a Pt-N4 single-atom catalyst prepared by electrochemical deposition and its bioelectrochemical application | |
CN114457365A (en) | Pt-Ni composite material, preparation method thereof and application thereof as catalyst for hydrogen production by electrolyzing water | |
CN111962099B (en) | Electrode for electrocatalytic production of hydrogen peroxide, preparation method and application thereof | |
CN116145193B (en) | Copper-based catalyst for electrocatalytic reduction of nitrate radical into ammonia and preparation method thereof | |
CN113235108A (en) | MXene supported noble metal cluster catalyst and preparation method and application thereof | |
CN117187872B (en) | Preparation method and electrocatalytic application of silver-imidazole complex and Ag composite material | |
Liu et al. | Two-dimension on two-dimension growth: hierarchical Ni 0.2 Mo 0.8 N/Fe-doped Ni 3 N nanosheet array for overall water splitting | |
CN111589459A (en) | Bifunctional catalyst for efficiently electrolyzing water, 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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |