CN117181182B - Recyclable copper-based hybrid material ethylene adsorbent and preparation method and application thereof - Google Patents
Recyclable copper-based hybrid material ethylene adsorbent and preparation method and application thereof Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000005977 Ethylene Substances 0.000 title claims abstract description 196
- 239000010949 copper Substances 0.000 title claims abstract description 144
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 143
- 239000000463 material Substances 0.000 title claims abstract description 142
- 239000003463 adsorbent Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 235000012055 fruits and vegetables Nutrition 0.000 claims abstract description 79
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 238000003860 storage Methods 0.000 claims abstract description 19
- 230000003213 activating effect Effects 0.000 claims abstract 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 36
- 240000005561 Musa balbisiana Species 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 19
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
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- 239000012046 mixed solvent Substances 0.000 claims description 8
- 244000183278 Nephelium litchi Species 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 3
- 244000298697 Actinidia deliciosa Species 0.000 claims description 2
- 235000009436 Actinidia deliciosa Nutrition 0.000 claims description 2
- 244000144725 Amygdalus communis Species 0.000 claims description 2
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 claims description 2
- 240000003259 Brassica oleracea var. botrytis Species 0.000 claims description 2
- 235000004936 Bromus mango Nutrition 0.000 claims description 2
- 240000006432 Carica papaya Species 0.000 claims description 2
- 235000009467 Carica papaya Nutrition 0.000 claims description 2
- 244000241257 Cucumis melo Species 0.000 claims description 2
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 claims description 2
- 235000011511 Diospyros Nutrition 0.000 claims description 2
- 244000236655 Diospyros kaki Species 0.000 claims description 2
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 2
- 244000070406 Malus silvestris Species 0.000 claims description 2
- 240000007228 Mangifera indica Species 0.000 claims description 2
- 235000014826 Mangifera indica Nutrition 0.000 claims description 2
- 235000011925 Passiflora alata Nutrition 0.000 claims description 2
- 235000000370 Passiflora edulis Nutrition 0.000 claims description 2
- 235000011922 Passiflora incarnata Nutrition 0.000 claims description 2
- 240000002690 Passiflora mixta Species 0.000 claims description 2
- 235000013750 Passiflora mixta Nutrition 0.000 claims description 2
- 235000013731 Passiflora van volxemii Nutrition 0.000 claims description 2
- 244000025272 Persea americana Species 0.000 claims description 2
- 235000008673 Persea americana Nutrition 0.000 claims description 2
- 240000005809 Prunus persica Species 0.000 claims description 2
- 235000006029 Prunus persica var nucipersica Nutrition 0.000 claims description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 2
- 244000017714 Prunus persica var. nucipersica Species 0.000 claims description 2
- 241000508269 Psidium Species 0.000 claims description 2
- 241000220324 Pyrus Species 0.000 claims description 2
- 240000003768 Solanum lycopersicum Species 0.000 claims description 2
- 235000009184 Spondias indica Nutrition 0.000 claims description 2
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims description 2
- 235000020224 almond Nutrition 0.000 claims description 2
- 235000021016 apples Nutrition 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
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- 230000036561 sun exposure Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 26
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
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- 238000012360 testing method Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
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- 235000021015 bananas Nutrition 0.000 description 12
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- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229920002494 Zein Polymers 0.000 description 5
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- 239000002699 waste material Substances 0.000 description 5
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
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- 229910021641 deionized water Inorganic materials 0.000 description 3
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- 239000002808 molecular sieve Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
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- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
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- 150000001880 copper compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- Storage Of Fruits Or Vegetables (AREA)
Abstract
The invention provides a recyclable copper-based hybrid material ethylene adsorbent, a preparation method and application thereof, wherein the copper-based hybrid material ethylene adsorbent is obtained by activating a copper-based hybrid material, and the average pore diameter of the copper-based hybrid material ethylene adsorbentThe average pore volume is 0.32-0.36cm 3g‑1. The copper-based hybrid material ethylene adsorbent is used for storage, fresh keeping, energy-saving storage and transportation of fruits and vegetables. The copper-based hybrid material ethylene adsorbent provided by the invention has high specific surface area, extremely large pore volume and high density coordination unsaturated metal sites, the average pore diameter is larger than the dynamic diameter of ethylene molecules, ethylene can easily enter into pore channels, further better contact between ethylene gas and the coordination unsaturated metal sites is facilitated, and the coordination unsaturated metal sites can easily interact with p electrons of double bonds in ethylene molecules to adsorb ethylene molecules, so that the ethylene adsorbent has very high ethylene adsorption performance.
Description
Technical Field
The invention relates to the technical field of fruit and vegetable and food preservation, in particular to a recyclable copper-based hybrid material ethylene adsorbent, and a preparation method and application thereof.
Background
Respiratory-transition type fruits and vegetables are prone to generate a large amount of ethylene gas during transportation and storage, and the ethylene can be combined with receptors on the surfaces of the fruits and vegetables to generate bitter compounds, which not only promote softening of the fruits and vegetables, but also gradually generate reddish brown spots on the fruits and vegetables, so that the fruits and vegetables gradually decay to significantly influence the quality of the fruits and vegetables, and serious economic losses are estimated to reach 750 hundred million yuan only in 2022 China. On the other hand, over 80% of fruits and vegetables in China are mainly subjected to normal-temperature logistics or natural logistics, so that the loss of the fruits and vegetables after picking is serious, the standardization of cold chain transportation in many areas is difficult to realize, and high energy is required to be consumed in the transportation and storage processes.
CN11065259a discloses an ethylene adsorbent, a preparation method and application thereof, and the method disperses monovalent copper compounds in the silicon aluminum phosphate molecular sieve through the spontaneous monolayer dispersion principle, thereby improving the ethylene adsorption effect. However, the ethylene adsorption capacity of the adsorbent prepared by the method is only 0.93-1.80mmol/g, the adsorption is not stable enough, the adsorption effect is not ideal enough, and the adsorbent is difficult to recycle, so that the application of the adsorbent in fruit and vegetable fresh-keeping is limited.
CN114052068a reports a biological film for ethylene adsorption and its application, which is prepared by mixing zein with ultrapure water solution of acetic acid to obtain zein-acetic acid solution, and then ultrasonic modifying to obtain ethylene adsorption biological film, and is applied to fruit and vegetable fresh-keeping. However, the ethylene adsorption biological film can not be recycled, and the preservation effect is not ideal enough, and the shelf life of the bananas can be prolonged by 1-2 days.
Commercial KMnO 4 particles have a remarkable effect on adsorbing ethylene gas, but KMnO 4 is irreversibly converted into strong oxidant MnO 2 during ethylene adsorption, thus being difficult to recycle and causing serious harm to the environment.
Therefore, the safe adsorbent which has high-efficiency ethylene adsorption and desorption performance and can be used for storing fruits and vegetables at normal temperature and keeping fresh is provided, the shelf life is prolonged, the long-term storage cost and energy consumption of the fruits and vegetables are obviously reduced, and the safe adsorbent becomes a key technical problem to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides a recyclable copper-based hybrid material ethylene adsorbent, and a preparation method and application thereof, so as to solve the problems of poor fresh-keeping effect, short fresh-keeping time, low-temperature fresh-keeping requirement and difficult recycling of the ethylene adsorbent in the existing fruit and vegetable fresh-keeping technology.
The technical scheme of the invention is realized as follows:
In a first aspect, the present invention provides a recyclable copper-based hybrid material ethylene adsorbent, the copper-based hybrid material ethylene adsorbent being activated by a copper-based hybrid material, the copper-based hybrid material ethylene adsorbent having an average pore size The average pore volume is 0.32-0.36cm 3g-1.
The copper-based hybrid material ethylene adsorbent provided by the invention has high specific surface area, extremely large pore volume and high density coordination unsaturated metal sites, and the average pore diameter is aboutGreater than the kinetic diameter of ethylene molecules/> Ethylene easily enters the pore canal, so that better contact between ethylene gas and a coordination unsaturated metal site is facilitated, the coordination unsaturated metal site can easily interact with p electrons of double bonds in ethylene molecules to adsorb ethylene, and the ethylene adsorbent is promoted to show high ethylene adsorption performance; meanwhile, the larger pore volume enables the copper-based hybrid material ethylene adsorbent to contain more ethylene molecules, so that the adsorption capacity is improved and the use amount of the adsorbent is reduced.
In a second aspect, the invention provides application of a recyclable copper-based hybrid material ethylene adsorbent, wherein the copper-based hybrid material ethylene adsorbent is used for storage and preservation of fruits and vegetables and energy-saving storage and transportation.
The mature fruits and vegetables can release ethylene gas to promote the self ripening and decay process, and the copper-based hybrid material ethylene adsorbent has moderate pore diameter and extremely large pore volume, can efficiently adsorb ethylene gas released by the fruits and vegetables, thereby slowing down the ripening and decay process of the fruits and vegetables; the ethylene adsorbent of the copper-based hybrid material can delay the ripening speed of fruits and vegetables and prolong the fresh-keeping period of the fruits and vegetables by adsorbing ethylene gas released by the fruits and vegetables, is very important for the storage and transportation of the fruits and vegetables, can reduce the loss and waste of the fruits and vegetables, and improves the quality and market value of the fruits and vegetables. In the process of storing and transporting fruits and vegetables, energy consumption and resource waste can be caused by the release of ethylene, and ethylene gas can be effectively adsorbed by using a copper-based hybrid material ethylene adsorbent, so that the energy consumption and the resource waste are reduced, and the energy-saving storage and transportation are realized; the copper-based hybrid material ethylene adsorbent has good regenerability, and can realize desorption of ethylene and regeneration of materials by adjusting temperature or other conditions, thereby realizing repeated use of the ethylene adsorbent and reducing environmental pollution and resource consumption.
On the basis of the technical scheme, preferably, the copper-based hybrid material ethylene adsorbent is used for storage, fresh-keeping, energy-saving storage and transportation of respiratory-transition fruits and vegetables. The respiratory-transition type fruits and vegetables release a large amount of ethylene when the fruits and vegetables are mature, so that the fruits and vegetables are mature, and compared with other types of fruits and vegetables, the fruits and vegetables have shorter shelf life and are easy to rot and deteriorate. The ethylene adsorbent of the copper-based hybrid material can effectively prolong the shelf life of the fruits and vegetables.
On the basis of the technical scheme, preferably, after the copper-based hybrid material ethylene adsorbent is used, the copper-based hybrid material ethylene adsorbent can be recycled after ethylene removal treatment, the ethylene removal treatment method comprises one of heat treatment at 60-180 ℃, sun exposure and ultraviolet lamp irradiation, and the ethylene removal treatment time is 1-10 h.
The copper-based hybrid material ethylene adsorbent can be regenerated by a pyrolysis method and the like, so that recycling is realized. Specifically, the ethylene adsorbent of the used copper-based hybrid material is subjected to heat treatment at 60-180 ℃, and the high temperature can increase the heat movement energy between the adsorbent and ethylene molecules so as to promote the adsorption ethylene molecules on the surface of the adsorbent to be desorbed; the used copper-based hybrid material adsorbent is exposed to the sun or irradiated by an ultraviolet lamp, so that the thermal movement energy between the adsorbent and ethylene molecules can be increased, and the adsorption state ethylene molecules on the surface of the adsorbent are promoted to be desorbed. The ethylene adsorbent of the copper-based hybrid material can be recycled, so that the use amount of the adsorbent can be reduced, and the fresh-keeping cost can be reduced.
On the basis of the technical scheme, preferably, the relational expression of the usage amount type of the copper-based hybrid material ethylene adsorbent and the fruit and vegetable type comprises:
wherein, The value is 0.9-1.1,/>The value is 9.5-10.5,/>The value is 99-101; /(I)The value is 18-22,/>The value is 26-29;
wherein y s represents the usage amount type of the copper-based hybrid material ethylene adsorbent, The type of the ethylene adsorbent used for the copper-based hybrid material is represented as low-usage amount,/>The type of the ethylene adsorbent used for the copper-based hybrid material is expressed as lower use amount, iThe type of the ethylene adsorbent used for the copper-based hybrid material is expressed as the medium used quantity,/>The type of the ethylene adsorbent used for the copper-based hybrid material is high, and n s represents the ethylene release amount of fruits and vegetables,/>A first threshold value of the ethylene release amount of the fruits and the vegetables is represented,Represents a second threshold value of the ethylene release amount of fruits and vegetables,/>A third threshold value of ethylene release amount of fruits and vegetables is represented, t s represents temperature,/>Representing a first threshold value of temperature,/>Representing a temperature second threshold.
On the basis of the above technical solution, preferably, the judging conditions of the usage amount type of the copper-based hybrid material ethylene adsorbent specifically include:
wherein, The value is 0.18-0.22,/>The value is 0.9-1.1,/>The value is 5.5-6.5;
In the method, in the process of the invention, Represents a first threshold value of the usage amount of the copper-based hybrid material ethylene adsorbent,/>Represents a second threshold value of the usage amount of the copper-based hybrid material ethylene adsorbent,/>A third threshold value of the usage amount of the copper-based hybrid material ethylene adsorbent is represented.
According to different ethylene release amounts of fruits and vegetables, different use amounts of ethylene adsorbents are adopted, so that the requirements of different fruits and vegetables can be better met, the shelf life of the fruits and vegetables can be prolonged, and the ripening and decay processes of the fruits and vegetables can be slowed down by adsorbing ethylene molecules in the fruits and vegetables through the special structure and the surface active sites of the adsorbents; simultaneously, the using amount of the ethylene adsorbent is accurately controlled according to different types of fruits and vegetables, so that the ethylene adsorption efficiency of the fruits and vegetables is ensured, and the waste of the ethylene adsorbent is avoided.
On the basis of the technical scheme, preferably, fruits and vegetables with low usage amount comprise cauliflower, persimmon and melon; fruits and vegetables with low usage amount include banana, mango, litchi, fig, guava and tomato; the fruit and vegetable used in the method comprises apples, pears, almonds, avocados, kiwi fruits, nectarines, papaya, peaches and plums; fruits and vegetables with high usage amount comprise Nanmei litchi and passion flower.
In a third aspect, the invention provides a method for preparing a recyclable copper-based hybrid material ethylene adsorbent,
S1, respectively preprocessing trimesic acid and copper acetate to obtain trimesic acid solution and copper acetate solution;
S2, stirring and reacting the trimesic acid solution and the copper acetate solution at 24-27 ℃, and centrifuging and drying to obtain the copper-based hybrid material;
And S3, grinding the copper-based hybrid material, and placing the ground copper-based hybrid material into a tube furnace for activation treatment to obtain the recyclable copper-based hybrid material ethylene adsorbent.
Based on the technical scheme, preferably, the stirring reaction in the step S2 is carried out at a rotating speed of 300-900rpm for 18-24 hours, and the reaction is carried out for 10-120 minutes after the reaction is finished. More preferably, the stirring reaction speed is 750rpm, the time is 24 hours, and the standing time is 30 minutes.
On the basis of the above technical solution, preferably, step S1 specifically includes: dissolving trimesic acid in a mixed solvent, and performing ultrasonic treatment to obtain a trimesic acid solution; dissolving copper acetate in a mixed solvent, and stirring and dispersing to obtain a copper acetate solution; the mixed solution consists of water, ethanol and N, N dimethylformamide.
On the basis of the technical scheme, preferably, the molar ratio of the trimesic acid to the copper acetate is 1:1-3, and the volume ratio of the water, the ethanol and the N, N-dimethylformamide of the mixed solution is 1-3:2-6:2-6.
The copper-based hybrid material is prepared at normal temperature and normal pressure, the principle is a dissolution-regrowth mechanism, N-dimethylformamide in a mixed solvent is used as an aprotic solvent, trimesic acid is deprotonated, copper acetate is partially dissolved in the mixed solvent, metal ions are restrained, and from the perspective of space time, the metal ions are released in a more controllable mode. The released cations will further coordinate with nearby available organic ligands and self-assemble into copper-based hybrid materials. At a substantial level, copper-based hybrid materials are thermodynamically more stable than copper acetate solids in the presence of ligands, which aids in metal release and serves as the primary driving force for subsequent chemical reactions.
Based on the above technical solution, preferably, the process conditions of the activation treatment in step S3 are as follows: under the inert atmosphere, the temperature is raised to 100-180 ℃ from 24-27 ℃ at the speed of 4.5-5.5 ℃/min, and the heat preservation is carried out for 2-10 h.
In the step S3, the specific surface area of the copper-based hybrid material can be increased and the adsorption performance of the copper-based hybrid material can be improved by grinding the copper-based hybrid material. The activation treatment can activate the copper-based hybrid material, increase the surface active sites of the copper-based hybrid material and improve the ethylene adsorption capacity, and under the inert atmosphere, the copper-based hybrid material can be promoted to generate structural change and form a certain number of surface active sites through heating and heat preservation reaction, so that the ethylene adsorption effect of the copper-based hybrid material is improved. Wherein, the too high activation temperature can damage the crystal structure and affect the ethylene adsorption performance; when the activation temperature is too low, impurities are difficult to remove, and then ethylene adsorption effect monitoring can be affected.
Compared with the prior art, the recyclable copper-based hybrid material ethylene adsorbent and the preparation method and application thereof have the following beneficial effects:
(1) The copper-based hybrid material ethylene adsorbent provided by the invention has high specific surface area, extremely large pore volume and high density coordination unsaturated metal sites, and the average pore diameter is about Greater than the kinetic diameter of ethylene molecules/> Ethylene easily enters the pore canal, so that better contact between ethylene gas and a coordination unsaturated metal site is facilitated, and the coordination unsaturated metal site can easily interact with p electrons of double bonds in ethylene molecules to adsorb ethylene, so that the ethylene adsorbent has high ethylene adsorption performance;
(2) The metal ions are firmly bonded with the organic ligand, the product stability is good, after the adsorbent is used, the interaction between the copper-based hybrid material and ethylene can be destroyed under certain conditions, the adsorbed ethylene is promoted to be desorbed, the recycling is further realized, and the recycled copper-based hybrid material ethylene adsorbent also shows high ethylene adsorption performance;
(3) The copper-based hybrid material ethylene adsorbent is applied to storage, fresh keeping, energy-saving storage and transportation of fruits and vegetables, and can efficiently adsorb ethylene gas released by fruits and vegetables, so that the ripening and decay processes of the fruits and vegetables are slowed down; by absorbing ethylene gas released by fruits and vegetables, the ripening speed of the fruits and vegetables can be delayed, the fresh-keeping period of the fruits and vegetables can be prolonged, the loss and waste in the storage and transportation of the fruits and vegetables can be reduced, and the quality and market value of the fruits and vegetables can be improved;
(4) According to the preparation method, the copper-based hybrid material of the crystal material is obtained through the coordination reaction of trimesic acid and copper acetate, the copper-based hybrid material is activated, the pore canal is opened at high temperature, the impurity atmosphere in the pore canal and inert gas are discharged together to obtain the ethylene adsorbent of the copper-based hybrid material, the preparation method is simple in steps and low in cost, the etching of strong acid and toxic reagents is avoided in the preparation process, the high temperature and high pressure are avoided, the environment is protected, and the realization of the large-scale preparation of the ethylene adsorbent of the copper-based hybrid material is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a copper-based hybrid material ethylene adsorbent prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of the copper-based hybrid material ethylene adsorbents prepared in example 1 and example 4 according to the present invention;
FIG. 3 is a graph showing the variation of ethylene concentration around bananas with different amounts of ethylene adsorbent used as copper-based hybrid material in experiment 1 for fruit and vegetable fresh-keeping application of the present invention;
Fig. 4 is a graph showing the change of ethylene concentration around bananas with KMnO 4 and the copper-based hybrid material ethylene adsorbent in the fruit and vegetable fresh-keeping application experiment 1 of the present invention;
FIG. 5 is a graph showing the change in ethylene concentration around bananas with KMnO 4 and copper-based hybrid material ethylene adsorbent in fruit and vegetable fresh-keeping application experiment 1 of the present invention;
Fig. 6 is a graph showing banana preservation effect in experiment 2 of fruit and vegetable preservation application of the present invention;
fig. 7 is a graph showing banana preservation effect in experiment 3 of fruit and vegetable preservation application of the present invention.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
In order to enable those skilled in the art to more clearly understand the technical solution of the present application, the technical solution of the present application will be described in detail below with reference to specific embodiments. If the experimental details are not specified in the examples, the conditions are generally conventional or recommended by the reagent company: reagents, consumables, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
The embodiment provides a recyclable copper-based hybrid material ethylene adsorbent and a preparation method thereof, and the recyclable copper-based hybrid material ethylene adsorbent specifically comprises the following steps:
S1, mixing 200mL of water, 200mL of ethanol and 200mLN, N-dimethylformamide to obtain a solution A; 9g of copper acetate (0.045 mol) is dissolved in 360mL of solution A, and the solution A is obtained by stirring and dispersing evenly at the stirring speed of 250 rpm; 6.3g of trimesic acid (0.030 mol) is dissolved in 240mL of solution A, the ultrasonic dispersion is uniform, the ultrasonic dissolution temperature is 25 ℃, the power is 100W, and the time is 6min, so as to obtain solution C;
S2, mixing the solution B and the solution C, stirring at a rotation speed of 750rpm/m for reaction for 24 hours at a temperature of 25 ℃, standing for 1 hour, centrifuging the reacted solution at a rotation speed of 10000rpm for 3 minutes, pouring out supernatant, adding 10mL of N, N-dimethylformamide for centrifuging again, repeating the centrifugal washing process for three times, adding 10mL of ethanol for centrifuging again, repeating the centrifugal washing process for three times, and finally placing the obtained solid into a vacuum drying box for vacuum drying at 90 ℃ for 12 hours to obtain the copper-based hybrid material;
S3, placing the copper-based hybrid material in a porcelain boat, transferring the porcelain boat into a tube furnace, continuously introducing Ar gas, heating to 180 ℃ at the speed of 5 ℃/min at the temperature of 25 ℃ for activation treatment, preserving heat for 8 hours, and cooling to room temperature along with the furnace to obtain the ethylene adsorbent of the copper-based hybrid material.
Example 2
The embodiment provides a recyclable copper-based hybrid material ethylene adsorbent and a preparation method thereof, and the recyclable copper-based hybrid material ethylene adsorbent specifically comprises the following steps:
S1, mixing 300mL of water, 400mL of ethanol and 400mLN, N-dimethylformamide to obtain a solution A; 6g of copper acetate (0.030 mol) is dissolved in 550mL of solution A, and the solution A is obtained by stirring and dispersing evenly at the stirring speed of 100 rpm; 6.3g of trimesic acid (0.030 mol) is dissolved in 550mL of solution A, the ultrasonic dispersion is uniform, the ultrasonic dissolution temperature is 25 ℃, the power is 200W, and the time is 10min, so as to obtain solution C;
S2, mixing the solution B and the solution C, stirring at a rotating speed of 300rpm/m for reaction for 18h at 25 ℃, standing for 20min, centrifuging the reacted solution at a rotating speed of 10000rpm for 3min, pouring out supernatant, adding 10mLN, N-dimethylformamide for centrifuging again, repeating the centrifugal washing process for three times, adding 10mL of ethanol for centrifuging again, repeating the centrifugal washing process for three times, and finally placing the obtained solid into a vacuum drying box for vacuum drying at 90 ℃ for 12h to obtain the copper-based hybrid material;
S3, placing the copper-based hybrid material in a porcelain boat, transferring the porcelain boat into a tube furnace, continuously introducing Ar gas, heating to 100 ℃ at the speed of 4.5 ℃/min at the temperature of 25 ℃ for activation treatment, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the ethylene adsorbent of the copper-based hybrid material.
Example 3
The embodiment provides a recyclable copper-based hybrid material ethylene adsorbent and a preparation method thereof, and the recyclable copper-based hybrid material ethylene adsorbent specifically comprises the following steps:
S1, mixing 50mL of water, 600mL of ethanol and 600mLN, N-dimethylformamide to obtain a solution A; 18g of copper acetate (0.090 mol) is dissolved in 940mL of solution A, and the solution A is obtained by stirring and dispersing uniformly at a stirring speed of 400 rpm; 6.3g of trimesic acid (0.030 mol) is dissolved in 310mL of solution A, the ultrasonic dispersion is uniform, the ultrasonic dissolution temperature is 25 ℃, the power is 50W, and the time is 3min, so as to obtain solution C;
S2, mixing the solution B and the solution C, stirring at a rotation speed of 900rpm/m for reaction for 20 hours at a temperature of 25 ℃, standing for 2 hours, centrifuging the reacted solution at a rotation speed of 10000rpm for 3 minutes, pouring out supernatant, adding 10mL of N, N-dimethylformamide for centrifuging again, repeating the centrifugal washing process for three times, adding 10mL of ethanol for centrifuging again, repeating the centrifugal washing process for three times, and finally placing the obtained solid into a vacuum drying box for vacuum drying at a temperature of 90 ℃ for 12 hours to obtain the copper-based hybrid material;
S3, placing the copper-based hybrid material in a porcelain boat, transferring the porcelain boat into a tube furnace, continuously introducing Ar gas, heating to 150 ℃ at the speed of 5.5 ℃/min at the temperature of 25 ℃ for activation treatment, preserving heat for 10 hours, and cooling to room temperature along with the furnace to obtain the ethylene adsorbent of the copper-based hybrid material.
Example 4
The embodiment provides a recyclable copper-based hybrid material ethylene adsorbent and a preparation method thereof, and the specific operation steps are the same as those of embodiment 1, and the difference is that: the reaction temperature was 30℃with stirring in step S2.
Example 5
The embodiment provides a recyclable copper-based hybrid material ethylene adsorbent and a preparation method thereof, and the specific operation steps are the same as those of embodiment 1, and the difference is that: in the step S3, the temperature is raised to 80 ℃ at a rate of 5 ℃/min at 25 ℃ for activation treatment.
Example 6
The embodiment provides a recyclable copper-based hybrid material ethylene adsorbent and a preparation method thereof, and the specific operation steps are the same as those of embodiment 1, and the difference is that: in the step S3, the temperature is raised to 200 ℃ at a rate of 5 ℃/min at 25 ℃ for activation treatment.
Example 7
The embodiment provides a recyclable copper-based hybrid material ethylene adsorbent and a preparation method thereof, and the specific operation steps are the same as those of embodiment 1, and the difference is that: in the step S1, copper nitrate is adopted to replace copper acetate.
Comparative example 1
This comparative example provides a biofilm for ethylene adsorption and its application, refer to patent CN114052068a, its preparation method comprises:
Measuring 20mL of 80% aqueous acetic acid solution by using a measuring cylinder, placing the measuring cylinder into a 100mL beaker, weighing 5g of zein powder by using an electronic analytical balance, adding the zein powder into the beaker filled with the aqueous acetic acid solution, adding a magnetic rotor, placing the beaker into a constant-temperature heating magnetic stirrer, heating and stirring in a water bath at 90 ℃ for 1h, standing and cooling at 25 ℃ until the zein is completely dissolved in the aqueous acetic acid solution. After cooling, adopting high field intensity ultrasonic waves with the ultrasonic power of 400W and the ultrasonic time of 0min, 5min, 15min and 60min to carry out modification treatment on the zein-acetic acid solution, wherein the temperature in the modification treatment process is kept constant at 20 ℃, and the modified zein solution is obtained.
Comparative example 2
The comparative example provides an Ag-SAPO-34@Cu-BTC composite material and a preparation and application method thereof, and the comparative example refers to patent CN115193408B and specifically comprises the following steps:
(1) Mixing 85wt% of phosphoric acid and deionized water, adding pseudo-boehmite under stirring, wherein the mass ratio of the pseudo-boehmite to the deionized water is 13:8:5, and continuously stirring for 1h to prepare a solution A; silver nitrate, silica sol, morpholine and ionized water are fully and uniformly mixed, the mass ratio of the silver nitrate to the silica sol to the morpholine is 2:1:2:4, solution B is prepared, and the solution B is dropwise added into the solution A by using a constant pressure funnel under stirring;
(2) Seed crystals are added into the solution, the mixture is fully stirred for 1h, then the mixture is transferred into a stainless steel reaction kettle with a 200mL polytetrafluoroethylene lining, crystallized for 48h at 200 ℃, washed by water after cooling and centrifugally separated, dried for 12h at 100 ℃, and then calcined by adopting a three-stage calcining process: stage 1, heating to 350 ℃ at a speed of 5 ℃/min, and preserving heat for 2 hours to decompose organic matters and form holes; stage 2, heating to 650 ℃ at a speed of 5 ℃/min, and preserving heat for 4 hours to decompose the active inorganic salt and form holes; stage 3 is to cool to 350 ℃ at 2 ℃/min, keep the temperature for 1h to avoid hole cracking, and then slowly cool to room temperature to prepare the Ag-SAPO-34 molecular sieve;
(3) Cu (NO 3)2·3H2 O, trimesic acid (H 3 BTC) and Ag-SAPO-34 molecular sieve are added into a mixed solution of DMF and deionized water according to a mass ratio of 6:3:1, the mixed solution is transferred into a polytetrafluoroethylene lining reaction kettle after being uniformly stirred, the reaction is carried out for 24 hours at 85 ℃, and after the reaction is finished, the products are sequentially subjected to centrifugation, water washing and drying treatment, thus obtaining the Ag-SAPO-34 1 @Cu-BTC composite adsorbent.
Fruit and vegetable fresh-keeping application experiment 1
The bananas are taken from the test group 1 in the same batch, the knife edges of the bananas are neatly taken down before use, the bananas are placed at a ventilation position for a period of time, and then the bananas are weighed to be close to each other, and then are respectively placed into a sealed transparent glass tank together with 0.2g, 0.4g and 0.6g of copper-based hybrid material ethylene adsorbent prepared in the embodiment 1, and are placed into a biochemical incubator to be subjected to heat preservation at 20 ℃, and the concentration is detected every 24 hours by an ethylene detector. Wherein, bananas are only added in the blank control group 1, and the KMnO 4 group 1 replaces the copper-based hybrid material ethylene adsorbent with 5g KMnO 4. Each set of experiments was repeated 3 times and averaged.
Fruit and vegetable fresh-keeping application experiment 2
The experiment uses a 5L transparent glass sealed tank as a container, the temperature is 20 ℃, and the specific grouping is as follows:
1) Blank control group 1:5L glass jar + banana;
2) Test group 1:5L glass jar+banana+0.2 g copper based hybrid ethylene adsorbent (example 1);
3) Test group 2:5L glass jar+banana+0.6g copper-based hybrid ethylene adsorbent (example 1);
4) Test groups 3-8: the same test group 2 was set, except that the copper-based hybrid material ethylene adsorbents were prepared by the methods in examples 2 to 7, respectively;
5) Control group 1-2: the same test group 2 was set, except that the adsorbents were prepared by the methods in comparative examples 1 to 2, respectively;
6) KMnO 4 control group 1:5L glass jar + banana +5g KMnO 4.
The fresh-keeping effect was observed on day 0, day 1, day 11, and day 14, respectively, and the banana storage time for each group of experiments is shown in table 1.
TABLE 1
Fruit and vegetable fresh-keeping experiment 3
The experiment uses a 5L transparent glass sealed tank as a container, the temperature is 20 ℃, and the specific grouping is as follows:
1) Blank control group 2:5L glass jar + banana;
2) Test group 8:5L glass jar+banana+0.6g copper-based hybrid ethylene adsorbent (example 1);
3) Test group 9:5L glass jar+banana+0.6g copper-based hybrid ethylene adsorbent (example 1) (1 h cycle at 70 ℃);
4) KMnO 4 control group 2:5L glass jar + banana +5g KMnO 4.
The fresh-keeping effect was observed on day 0, day 1, day 11, and day 14, respectively, and the banana storage time for each group of experiments is shown in table 2.
TABLE 2
FIG. 1 shows XRD patterns of the copper-based hybrid material and the ethylene adsorbent of the copper-based hybrid material prepared in example 1 of the present invention, and it can be seen that the crystal forms of the obtained materials are not changed before and after activation at 180 ℃. Through testing, the pore volume of the copper-based hybrid material obtained in the embodiment is 0.323cm 3g-1, and the pore volume of the copper-based hybrid material after activation at 180 ℃ is 0.339cm 3 g-1, which shows that the pore structure of the copper-based hybrid material has small change before and after activation.
FIG. 2 shows XRD patterns of the copper-based hybrid material ethylene adsorbent prepared in example 1 and the copper-based hybrid material ethylene adsorbent prepared in example 4, wherein the reaction is carried out at 25 ℃, the XRD patterns show sharper peaks, and the copper-based hybrid material ethylene adsorbent has good crystallinity. And when the reaction is carried out at 30 ℃, the XRD obvious peak is more miscellaneous, and the peak is not sharp, which shows that the crystallinity of the ethylene adsorbent of the copper-based hybrid material is poor.
Fig. 3, fig. 4 and fig. 5 show graphs of the ethylene concentration change around the banana when the fruit and vegetable fresh-keeping application experiment 1 is performed with different amounts of copper-based hybrid material ethylene adsorbent, blank control and KMnO 4. As can be seen from the curves of the ethylene concentration around the bananas in fig. 3, 4 and 5, the copper-based hybrid material ethylene adsorbent can be used for adsorbing the ethylene released from the bananas. With the increase of the dosage of the copper-based hybrid material ethylene adsorbent, the concentration of ethylene around the banana becomes lower, the larger the dosage is, the more obvious the adsorption effect is, and when the dosage of the copper-based hybrid material ethylene adsorbent is 0.2-0.4g, the adsorption effect on ethylene around the banana is similar. However, when the copper-based hybrid material ethylene adsorbent was used in an amount of 0.6g, the adsorption effect was close to that of the conventional ethylene adsorbent KMnO 4.
Fig. 6 shows the effects of the fruit and vegetable fresh-keeping application experiment 2 of the blank control group 1, the test group 2 and the KMnO 4 control group 1, as can be seen from fig. 6, the fresh-keeping experiment is carried out on the fruits and vegetables with bananas as the representative fruits and vegetables, and the fresh-keeping effect of the copper-based hybrid material ethylene adsorbent is better than that of commercial KMnO 4. Wherein the blank control group 1 showed significant large rot, the test group 1 showed only small spots, the test group 2 showed a large black spot, but no rot, and the KMnO 4 control group 1 showed only small black spots. The effect was most pronounced at 15 days, the blank had completely decayed, the test group 1 had increased spots, no significant change in test group 2 occurred, and the KMnO 4 control had increased spots. Therefore, the recyclable copper-based hybrid material ethylene adsorbent has a good fresh-keeping effect.
Fig. 7 shows the effects of the fruit and vegetable fresh-keeping application experiment 3 of the blank control group 2, the test group 8, the test group 9 and the KMnO 4 control group 2, and as can be seen from fig. 7, the effect of the recycled copper-based hybrid material ethylene adsorbent for banana fresh-keeping is similar to that of the fresh copper-based hybrid material ethylene adsorbent. At day 11: blank control group 2 became black, test group 8 did not show significant change, test group 9 showed only a few spots, KMnO 4 control group 2 did not show significant change; the effect is most obvious on day 14: the blank had completely decayed, no significant change occurred in test group 8, the spots increased in test group 9, and the KMnO 4 control also decayed to black. Therefore, the copper-based hybrid material ethylene adsorbent can be recycled.
As can be seen from Table 1, by comparing the blank control group 1, the test groups 1-4, the control groups 1-3 and the KMnO 4 control group 1, the copper-based hybrid material ethylene adsorbent prepared by the invention has better fruit and vegetable fresh-keeping effect, and can prolong the storage time by 1-6 days compared with the condition without the fresh-keeping agent; compared with the existing preservative (such as control groups 1 and 2 and KMnO 4), the preservation time can be prolonged by 1-2 days, and the preservation effect is better. As shown by comparison of test groups 2-8, the fresh-keeping effect of the prepared copper-based hybrid material ethylene adsorbent can be influenced by the over-high stirring reaction temperature and the over-high or over-low activation temperature and the change of the preparation raw materials in the preparation process.
From table 2, comparison of blank control group 2, test group 8, test group 9 and KMnO 4 control group 2 shows that the banana preservation effect of the recycled copper-based hybrid material ethylene adsorbent is similar to that of the new copper-based hybrid material ethylene adsorbent.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (5)
1. A recyclable copper-based hybrid material ethylene adsorbent is characterized in that: the copper-based hybrid material ethylene adsorbent is obtained by activating a copper-based hybrid material, wherein the average pore diameter of the copper-based hybrid material ethylene adsorbent is 8-10A, and the average pore volume is 0.32-0.36 cm 3g-1;
The copper-based hybrid material ethylene adsorbent is used for storage, fresh keeping, energy-saving storage and transportation of fruits and vegetables;
the copper-based hybrid material ethylene adsorbent can be recycled after being treated by removing ethylene, wherein the ethylene removing treatment method comprises one of heat treatment at 60-180 ℃, sun exposure and ultraviolet lamp irradiation, and the ethylene removing treatment time is 1-10 h;
The relational expression of the usage amount type of the copper-based hybrid material ethylene adsorbent and the fruit and vegetable type comprises:
；
wherein, The value is 0.9-1.1,/>The value is 9.5-10.5,/>The value is 99-101; /(I)Take the value of 18-22 of the total number of the components,The value is 26-29;
In the method, in the process of the invention, Represents the usage amount type of the copper-based hybrid material ethylene adsorbent,/>The type of the ethylene adsorbent used for the copper-based hybrid material is represented as low-usage amount,/>The type of the ethylene adsorbent used for the copper-based hybrid material is represented as a lower use amount,The type of the ethylene adsorbent used for the copper-based hybrid material is expressed as the medium used quantity,/>The type of the ethylene adsorbent used for representing the copper-based hybrid material is highIndicates the ethylene release amount of fruits and vegetables,/>A first threshold value of the ethylene release amount of the fruits and the vegetables is represented,Represents a second threshold value of the ethylene release amount of fruits and vegetables,/>Represents a third threshold value of ethylene release amount of fruits and vegetables,/>Representing temperature,/>Representing a first threshold value of temperature,/>Representing a temperature second threshold;
the preparation method of the recyclable copper-based hybrid material ethylene adsorbent comprises the following steps:
S1, respectively preprocessing trimesic acid and copper acetate to obtain trimesic acid solution and copper acetate solution;
s2, stirring and reacting the trimesic acid solution and the copper acetate solution at 24-27 ℃, and centrifuging and drying to obtain the copper-based hybrid material, wherein the reaction time is 18-24 hours;
s3, grinding the copper-based hybrid material, and then placing the ground copper-based hybrid material into a tube furnace for activation treatment to obtain a recyclable copper-based hybrid material ethylene adsorbent;
The process conditions of the activation treatment in the step S3 are as follows: heating to 100-180deg.C at a rate of 5deg.C/min from 24-27deg.C under inert atmosphere, and maintaining the temperature for 2-10 h.
2. A recyclable copper-based hybrid material ethylene adsorbent as defined in claim 1, wherein: the judging conditions of the usage amount type of the copper-based hybrid material ethylene adsorbent specifically comprise:
；
wherein, The value is 0.18-0.22,/>The value is 0.9-1.1,/>The value is 5.5-6.5;
In the method, in the process of the invention, Represents a first threshold value of the usage amount of the copper-based hybrid material ethylene adsorbent,/>Represents a second threshold value of the usage amount of the copper-based hybrid material ethylene adsorbent,/>A third threshold value of the usage amount of the copper-based hybrid material ethylene adsorbent is represented.
3. A recyclable copper-based hybrid material ethylene adsorbent as defined in claim 1, wherein: the low-consumption fruits and vegetables comprise cauliflower, persimmon and melon; fruits and vegetables with low usage amount include banana, mango, fig, guava and tomato; the fruit and vegetable used in the method comprises apples, pears, almonds, avocados, kiwi fruits, nectarines, papaya, peaches and plums; fruits and vegetables with high usage amount comprise Nanmei litchi and passion flower.
4. A recyclable copper-based hybrid material ethylene adsorbent as defined in claim 1, wherein: the step S1 specifically comprises the following steps: dissolving trimesic acid in a mixed solvent, and performing ultrasonic treatment to obtain a trimesic acid solution; dissolving copper acetate in a mixed solvent, and stirring and dispersing to obtain a copper acetate solution; the mixed solvent consists of water, ethanol and N, N-dimethylformamide.
5. A recyclable copper-based hybrid material ethylene adsorbent as defined in claim 4, wherein: the molar ratio of trimesic acid to copper acetate is 1:1-3, and the volume ratio of water, ethanol and N, N-dimethylformamide of the mixed solvent is 1-3:2-6:2-6.
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