CN115779878A - Method for restoring adsorption activity of non-porous self-adaptive crystal material by pressure - Google Patents
Method for restoring adsorption activity of non-porous self-adaptive crystal material by pressure Download PDFInfo
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- CN115779878A CN115779878A CN202211578480.0A CN202211578480A CN115779878A CN 115779878 A CN115779878 A CN 115779878A CN 202211578480 A CN202211578480 A CN 202211578480A CN 115779878 A CN115779878 A CN 115779878A
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000000694 effects Effects 0.000 title claims abstract description 24
- 239000013078 crystal Substances 0.000 title claims abstract description 18
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 5
- 239000010959 steel Substances 0.000 claims abstract description 5
- 238000007373 indentation Methods 0.000 claims abstract description 4
- 239000004005 microsphere Substances 0.000 claims abstract description 4
- 239000010979 ruby Substances 0.000 claims abstract description 4
- 229910001750 ruby Inorganic materials 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000004080 punching Methods 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims description 4
- 230000003044 adaptive effect Effects 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 16
- 238000000862 absorption spectrum Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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Abstract
The invention discloses a method for recovering the adsorption activity of a non-porous self-adaptive crystal material by pressure, belonging to the field of research on solid adsorption materials. The method comprises the following steps: firstly, prepressing a T301 steel sheet, punching a hole in the center of an indentation by utilizing laser to serve as a sample cavity, adding ruby microspheres serving as a pressure calibration object into the sample cavity, then putting a sample to be recovered, sealing an upper cover of a press, pressurizing to 17.5GPa, then unloading the pressure to normal pressure, recovering the site activity of the sample, wherein the sample to be recovered is in a porous state after being adsorbed by a non-porous self-adaptive crystal material. The invention avoids the defects of high environmental requirement, difficult operation and high energy consumption of the traditional vacuum heating desorption molecular method, fundamentally avoids the problem of thermal polymerization, and is a brand-new green means for effectively regulating and recovering the activity of the adsorption sites.
Description
Technical Field
The invention belongs to the field of research on solid-state adsorption materials, and particularly relates to a brand-new simple method for effectively regulating and recovering the activity of an adsorption site of a non-porous self-adaptive crystal material through the mechanical action of a press.
Background
The solid adsorption material is widely applied to a plurality of fields of molecular recognition, product separation, environmental pollution treatment and the like due to the unique adsorption performance, and is an important component for environmental protection and solving the energy problem. After the molecules are adsorbed, how to effectively desorb the molecules, recover the activity of adsorption sites and prolong the continuous cycle service life is very important for the application of solid adsorption materials. The solid-state adsorption material mostly adopts a heating mode to desorb molecules to recover the activity of adsorption sites, and separates, recovers and utilizes pollution molecules and molecules which can be used as energy. However, the heating method often requires a pure vacuum environment, and the micro-nano-sized adsorbent material also has a problem of thermal aggregation, which deteriorates the adsorption performance of the material. The method for recovering the activity of the adsorption sites by exploring a more stable, reliable, pure and convenient way is the key point of the research of the solid adsorption material. The pressure is used as a pure and green technology, can effectively change the inter-molecular distance and relative position, regulates the inter-molecular interaction, has great potential in the aspects of regulating and activating the activity of adsorption sites, and is an important potential means for regulating and efficiently recovering the adsorption performance of the solid adsorbent.
The non-porous self-adaptive crystal material is an active crystal based on a large ring, is also a novel solid adsorption and separation material, and has excellent adsorption performance. The material has self-adaptive capacity to objects, is easy to prepare in a large scale, has good stability, and shows good application potential in the aspects of adsorption separation of hydrocarbons and environmental improvement. The P5-PDI is a novel non-porous self-adaptive crystal material, is formed by non-covalent bonding of the pillar aromatic hydrocarbon P5 and Perylene Diimide (PDI), and can effectively detect and recover various organic matters such as alkyl halide and the like. In the initial state, the material is in a non-porous state (P5-PDI alpha) when no molecules are adsorbed; when a target molecule, such as THF, is adsorbed to the PDI site of the material, the sample is converted to a porous state. The adsorbed molecules affect the charge transfer interaction between P5 and PDI to form a charge transfer state (CT), and a strong CT absorption peak is formed in the absorption spectrum, which significantly changes the color of the material from the initial colorless state to the red/orange of the adsorbed state. Taking THF as an example: when THF is adsorbed to PDI to form P5-PDI, an obvious CT absorption peak is formed in the range of 455-550nm of an absorption spectrum, and the color of the material is changed from white to orange; when THF is desorbed from PDI site, CT absorption peak at 455-550nm in absorption spectrum disappears, orange color of the material gradually fades and fades, and activity of PDI site is recovered. For the P5-PDI material, the desorption of THF molecules is realized by continuously heating at 75 ℃ for 12 hours in a vacuum environment. However, the method not only needs a special vacuum environment, but also has long time consumption and large energy consumption, thereby limiting the practical application of the method. The pressure can effectively regulate the intermolecular interaction and is a potential means for recovering the P5-PDI adsorption activity. However, a method for recovering the activity of the P5-PDI adsorption site by a mechanical action such as pressure has not been reported yet.
Disclosure of Invention
The invention aims to provide a method for restoring the adsorption site activity of a non-porous self-adaptive crystal material through pressure.
The specific technical scheme of the invention is as follows:
a method for restoring the adsorption activity of a non-porous adaptive crystal material by pressure is characterized in that diamond anvil is used for applying pressure to the material, and the method comprises the following steps: the method comprises the steps of firstly pre-pressing a T301 steel sheet, punching a hole in the center of an indentation by utilizing laser to serve as a sample cavity, adding ruby microspheres in the sample cavity to serve as a pressure calibration object, then putting a sample to be recovered, sealing an upper cover of a press, pressurizing to 17.5GPa, then unloading the pressure to normal pressure, recovering the site activity of the sample, wherein the sample to be recovered is in a porous state after being adsorbed by a non-porous self-adaptive crystal material.
Preferably, the sample to be recovered is a THF-adsorbed P5-PDI crystal, and THF molecules are adsorbed after the non-covalent bonding of the pillar arene P5 and PDI, and the molecular structure is shown as follows:
during the pressure relief process, the color of the material changes from orange red to light yellow, and the intensity of the CT peak at 540nm in the absorption spectrum gradually decreases until the CT peak basically disappears. This indicates that THF is gradually desorbed from the PDI site and PDI site activity is effectively restored.
Compared with the prior art, the invention has the following beneficial effects:
(1) The recovery of the activity of the PDI adsorption site in P5-PDI is effectively realized through pressure, the color of the material is changed from orange to yellow in the pressure relief process, the absorption spectrum shows that the CT absorption peak is gradually weakened, the CT peak is reduced to 0.13 percent under 17.5GPa after pressure relief, and THF is desorbed from the PDI site.
(2) The novel method for conveniently and effectively recovering the activity of the adsorption sites of the non-porous self-adaptive crystal material is provided, the defects of high environmental requirement, difficulty in operation and high energy consumption of the traditional vacuum heating molecular desorption method are overcome, the problem of thermal polymerization is fundamentally avoided, and the method is a brand-new green means for effectively regulating and recovering the activity of the adsorption sites.
Drawings
FIG. 1 is a high pressure in situ optical photograph of the pressure relief process of the P5-PDI material of example 1.
FIG. 2 is the high pressure in situ UV-VIA absorption spectrum of the pressure relief process of the P5-PDI material of example 1.
FIG. 3 is a curve of the 540nm CT absorption peak intensity of the pressure relief process absorption spectrum of the P5-PDI material in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1: demonstration of pressure recovery PDI site adsorptive Activity
A diamond anvil with the anvil surface diameter of 300 mu m is selected as a pressurizing device, a T301 steel sheet is firstly pre-pressed, the thickness of the pre-pressed steel sheet is 50 mu m, and a small hole with the diameter of 120 mu m is punched at the center of an indentation by laser to be used as a sample cavity. Adding ruby microspheres as a pressure calibration object, then putting P5-PDI crystal particles, sealing the upper cover of a press, and pressurizing to 17.51GPa. The pressure was then relieved to return to atmospheric pressure. During the pressure relief process, when the pressure is reduced to below 8.29GPa, the color of the sample gradually changes from orange to yellow along with the gradual reduction of the pressure, as shown in the attached figure 1 (since the patent application document does not support color, the figure 1 is only shown in black and white format); the high pressure in situ UV-visible absorption spectrum of the pressure relief process is shown in FIG. 2, and the intensity of the CT absorption peak at 540nm in the absorption spectrum gradually decreases with decreasing pressure, as shown in FIG. 3, indicating that the intramolecular CT state formed by the adsorption of THF at the PDI site gradually decreases, i.e., the THF molecule desorbs from the PDI site during the pressure relief process. The pressure is relieved to normal pressure, the sample becomes light yellow, the intensity of a CT peak at 540nm in an absorption spectrum is reduced to 0.13 percent of that of the CT peak at 17.51GPa, and the activity of a PDI adsorption site is effectively recovered.
The foregoing description illustrates and describes embodiments of the present invention, and therefore, the present invention should not be limited by the above description, but rather by the scope of the present invention.
Claims (2)
1. A method for restoring the adsorption activity of a non-porous adaptive crystal material by pressure is characterized in that diamond anvil is used for applying pressure to the material, and the method comprises the following steps: the method comprises the steps of firstly pre-pressing a T301 steel sheet, punching a hole in the center of an indentation by utilizing laser to serve as a sample cavity, adding ruby microspheres in the sample cavity to serve as a pressure calibration object, then putting a sample to be recovered, sealing an upper cover of a press, pressurizing to 17.5GPa, then unloading the pressure to normal pressure, recovering the site activity of the sample, wherein the sample to be recovered is in a porous state after being adsorbed by a non-porous self-adaptive crystal material.
2. The method for pressure recovery of the adsorption activity of the non-porous adaptive crystal material according to claim 1, wherein the sample to be recovered is a THF-adsorbed P5-PDI crystal, and the THF molecules are adsorbed after the non-covalent bonding of the pillared aromatic hydrocarbon P5 and PDI, and the molecular structure is schematically shown as follows:
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211578480.0A CN115779878A (en) | 2022-12-09 | 2022-12-09 | Method for restoring adsorption activity of non-porous self-adaptive crystal material by pressure |
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| CN202211578480.0A CN115779878A (en) | 2022-12-09 | 2022-12-09 | Method for restoring adsorption activity of non-porous self-adaptive crystal material by pressure |
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Citations (8)
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| US4762010A (en) * | 1987-04-02 | 1988-08-09 | Mobil Oil Corporation | Apparatus and method for adsorption and desorption studies, particularly for characterization of catalysts |
| RU2168360C2 (en) * | 1999-07-12 | 2001-06-10 | Кузнецов Леонид Григорьевич | Adsorbent regeneration process |
| CN1761520A (en) * | 2003-01-28 | 2006-04-19 | 环境清洁技术公司 | Oxides of manganese processed in continuous flow reactors |
| CN103965865A (en) * | 2014-05-05 | 2014-08-06 | 吉林大学 | Preparation method and application of piezochromic material |
| CN105973678A (en) * | 2016-07-15 | 2016-09-28 | 吉林大学 | Device and method for transferring two-dimensional layered semiconductor material to diamond anvil cell |
| CN110364227A (en) * | 2019-07-18 | 2019-10-22 | 中国石油大学(华东) | A kind of mud shale supercritical methane isotherm adsorption model based on variable density |
| CN110438569A (en) * | 2019-08-22 | 2019-11-12 | 浙江大学 | A kind of non-porous adaptivity organic fluorescence crystalline material and its preparation method and application |
| CN112206756A (en) * | 2020-10-22 | 2021-01-12 | 广东华特气体股份有限公司 | Desorption method of adsorbent |
-
2022
- 2022-12-09 CN CN202211578480.0A patent/CN115779878A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762010A (en) * | 1987-04-02 | 1988-08-09 | Mobil Oil Corporation | Apparatus and method for adsorption and desorption studies, particularly for characterization of catalysts |
| RU2168360C2 (en) * | 1999-07-12 | 2001-06-10 | Кузнецов Леонид Григорьевич | Adsorbent regeneration process |
| CN1761520A (en) * | 2003-01-28 | 2006-04-19 | 环境清洁技术公司 | Oxides of manganese processed in continuous flow reactors |
| CN103965865A (en) * | 2014-05-05 | 2014-08-06 | 吉林大学 | Preparation method and application of piezochromic material |
| CN105973678A (en) * | 2016-07-15 | 2016-09-28 | 吉林大学 | Device and method for transferring two-dimensional layered semiconductor material to diamond anvil cell |
| CN110364227A (en) * | 2019-07-18 | 2019-10-22 | 中国石油大学(华东) | A kind of mud shale supercritical methane isotherm adsorption model based on variable density |
| CN110438569A (en) * | 2019-08-22 | 2019-11-12 | 浙江大学 | A kind of non-porous adaptivity organic fluorescence crystalline material and its preparation method and application |
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Non-Patent Citations (3)
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