CN116550290B - Calcium chloride cluster anchored MOFs derived porous adsorbent and preparation method and application thereof - Google Patents
Calcium chloride cluster anchored MOFs derived porous adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN116550290B CN116550290B CN202310445127.3A CN202310445127A CN116550290B CN 116550290 B CN116550290 B CN 116550290B CN 202310445127 A CN202310445127 A CN 202310445127A CN 116550290 B CN116550290 B CN 116550290B
- Authority
- CN
- China
- Prior art keywords
- calcium chloride
- mofs
- calcium
- anchored
- porous adsorbent
- 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
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 82
- 239000003463 adsorbent Substances 0.000 title claims abstract description 71
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 title claims abstract description 40
- 239000001110 calcium chloride Substances 0.000 title claims abstract description 28
- 229910001628 calcium chloride Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 239000011575 calcium Substances 0.000 claims abstract description 35
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 31
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 39
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 37
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 37
- 238000000197 pyrolysis Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 22
- 238000010025 steaming Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 64
- 238000003795 desorption Methods 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229960005069 calcium Drugs 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 229960002713 calcium chloride Drugs 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000011065 in-situ storage Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 7
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010952 in-situ formation Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- WMFHUUKYIUOHRA-UHFFFAOYSA-N (3-phenoxyphenyl)methanamine;hydrochloride Chemical compound Cl.NCC1=CC=CC(OC=2C=CC=CC=2)=C1 WMFHUUKYIUOHRA-UHFFFAOYSA-N 0.000 description 1
- YNZDQQMTXDYPLK-UHFFFAOYSA-N 2,5-bis(2H-tetrazol-5-yl)terephthalic acid Chemical compound N=1NN=NC=1C1=C(C(=O)O)C=C(C(=C1)C(=O)O)C=1N=NNN=1 YNZDQQMTXDYPLK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03B—INSTALLATIONS OR METHODS FOR OBTAINING, COLLECTING, OR DISTRIBUTING WATER
- E03B3/00—Methods or installations for obtaining or collecting drinking water or tap water
- E03B3/28—Methods or installations for obtaining or collecting drinking water or tap water from humid air
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a calcium chloride cluster anchored MOFs derivative porous adsorbent and a preparation method thereof, and the preparation method comprises the following steps: (1) Placing Ca-MOF in inert gas atmosphere, pyrolyzing at 300-800 ℃ for 5-24h, and marking as calcium-containing porous carbon PC; (2) And (3) treating the calcium-containing porous carbon PC with HCl steam for 5-24h, and drying to obtain the calcium chloride cluster anchored MOFs derivative porous adsorbent. The invention also discloses application of the calcium chloride cluster anchored MOFs derivative porous adsorbent in atmospheric water collection. The calcium chloride cluster anchored MOFs derivative porous adsorbent has higher adsorption capacity, excellent photothermal conversion capability and rapid adsorption and desorption kinetics, and can be applied to the whole humidity range (10-100%), especially the atmospheric water collection in typical drought climates.
Description
Technical Field
The invention relates to the technical field of porous adsorbents, in particular to a calcium chloride cluster anchored MOFs derivative porous adsorbent, and a preparation method and application thereof.
Background
Water resources are vital to life. However, water resource maldistribution and demand in many areas are increasing, which greatly affects the health and well-being of people. For emergency or remote arid areas, it is critical to develop stable and sustainable fresh water supply technologies. Atmospheric water exists in the form of water vapor or droplets and is a rich resource. Mist collection, refrigeration technology, and adsorption-based atmospheric water collection (SAWH) methods have attracted extensive research interest over the past decade. The solar-driven SAWH can capture moisture from ambient air at any time and release the moisture in sunlight, and is considered as an energy-saving and clean fresh water acquisition method.
There are a variety of adsorbents currently used for SAWH, such as carbon materials, hygroscopic salts, and metal organic framework Materials (MOFs). The carbon material has ultrahigh porosity and chemical stability, is suitable for the gas adsorption field, but has the problems of weak water affinity and insufficient low-humidity adsorption capacity. Deliquescent salts, such as lithium chloride (LiCl) and calcium chloride (CaCl 2), exhibit high adsorption capacities in different environments, but are difficult to recover and cause environmental pollution. Although this problem is solved by preparing a complex salt adsorbent, the adsorption kinetics and cycle stability of the complex salt still need to be improved. In contrast, MOFs materials have a large specific surface area, rich adsorption sites, and rapid adsorption and desorption kinetics, and are considered to be the most promising next generation water absorbing agents. However, most MOFs materials with poor light absorption capability cannot reach high temperature in sunlight, resulting in low desorption efficiency and insufficient daily water yield.
Solar driven SAWH performance is closely related to the water absorption capacity and kinetics of the adsorbent. At present, researchers increase the adsorption capacity of MOFs adsorbents by means of structural design to increase pore volume or complexing with deliquescent salts, and the like. However, the increase in porosity affects the hydrophilicity and stability of the scaffold, the limited pore volume limits the maximum loading of deliquescent salt, and in addition, there are deliquescent salt agglomeration and leakage problems. For realizing rapid water adsorption-desorption kinetics, researchers prepare the adsorbent with high hydrophilicity and photo-thermal property by a strategy of post-synthesis modification or pyrolysis of MOFs material, and the adsorbent can realize multiple circulation, but also has the problems of insufficient low-humidity water absorption capacity, low daily water yield and the like.
In order to overcome the limitations of the above conditions, it is necessary to explore a new method for synthesizing an adsorbent based on MOFs materials with high water absorbability and excellent photo-thermal properties, and finally realizing multiple adsorption and desorption cycles, improving daily water yield, and solving the problem of lack of fresh water resources.
Disclosure of Invention
The invention provides a calcium chloride cluster anchored MOFs derivative porous adsorbent and a preparation method thereof, wherein the metal organic framework derivative porous adsorbent has higher adsorption capacity, excellent photothermal conversion capability and rapid adsorption and desorption kinetics, and can be applied to the whole humidity range (10-100%), in particular to the atmospheric water collection in a typical desert climate.
The technical scheme of the invention is as follows:
A method for preparing a calcium chloride cluster anchored MOFs-derived porous adsorbent, comprising the steps of:
(1) Placing Ca-MOF in inert gas atmosphere, pyrolyzing at 300-800 ℃ for 5-24h, and marking as calcium-containing porous carbon PC;
(2) And (3) treating the calcium-containing porous carbon PC with HCl steam for 5-24h, and drying to obtain the calcium chloride cluster anchored MOFs derivative porous adsorbent.
Ca-MOF is a metal-organic framework material with a abundance of metal Ca ions. Ca-MOFs can be prepared using methods disclosed in the prior art.
In the preparation method, the Ca-MOF material can be converted into the porous carbon with excellent photo-thermal property and abundant porosity in the pyrolysis process, and the subsequent HCl steam treatment process can form the calcium chloride cluster anchored porous adsorbent in situ through the strong interaction of Cl ions and calcium ions in the porous carbon skeleton, so that the porous adsorbent has high adsorption capacity and rapid adsorption and desorption kinetics.
Pyrolysis temperature affects the composition and crystallinity of the calcium-containing porous carbon PC. When the pyrolysis temperature is too low, the Ca-MOF structure is not destroyed, and calcium-containing porous carbon PC cannot be formed; as the pyrolysis temperature increases or the pyrolysis time increases, calcium carbonate crystals are gradually formed, which is detrimental to the subsequent in situ formation of metal salt anchored porous adsorbents.
Preferably, in the step (1), the pyrolysis temperature is 300-500 ℃ and the pyrolysis time is 5-24h.
Further preferably, the pyrolysis temperature is 350-450 ℃ and the pyrolysis time is 5-12h.
Most preferably, the pyrolysis temperature is 400℃and the pyrolysis time is 5 hours.
HCl steaming time can affect the crystallinity and water adsorption properties of the metal organic framework-derived porous adsorbent. When the steam treatment time is shorter, calcium chloride dihydrate crystals are not formed, the prepared metal organic framework derivative porous adsorbent only presents a diffraction peak of amorphous carbon, and the calcium chloride cluster anchored porous adsorbent is obtained through in-situ reaction, but the water adsorption capacity of the adsorbent is lower at the moment; along with the extension of the steam treatment time, calcium chloride dihydrate crystals are gradually formed, which is not beneficial to in-situ anchoring of calcium chloride clusters and affects the adsorption and desorption kinetics of the prepared metal organic framework-derived porous adsorbent.
Thus, preferably, in step (2), the HCl steaming time is 12-24 hours; most preferably, the HCl steaming time is 24 hours. Further preferably, step (1) includes: the Ca-MOF is placed in an inert gas atmosphere and pyrolyzed for 5 to 12 hours at the temperature of 350 to 450 ℃.
Further preferably, step (2) includes: and (3) sealing the calcium-containing porous carbon PC in a container containing a concentrated hydrogen chloride solution, treating the calcium-containing porous carbon PC for 5-24 hours by adopting HCl steam, and drying to obtain the metal organic framework derivative porous adsorbent.
Further preferably, the mass concentration of the concentrated hydrogen chloride solution is 36% -38%.
The porous carbon skeleton formed by the pyrolysis process has high porosity and pore volume, and provides a large amount of pore space for uniform anchoring of calcium chloride clusters. In addition, the formed hierarchical porous structure is beneficial to heat transfer and mass transfer, promotes sufficient contact between the adsorbent and water molecules, and improves adsorption and desorption kinetics. The calcium chloride cluster anchored porous adsorbent is formed in situ by the HCl steaming process. Unlike the conventional method for preparing composite salt, the porous matrix (such as porous carbon, MOFs material, aerogel) and the like are directly immersed into the salt solution, so that the problems of salt aggregation and leakage exist. The preparation method of the invention directly converts the calcium source in Ca-MOF into calcium chloride clusters in situ instead of calcium chloride crystals, thereby effectively preventing salt leakage and improving adsorption kinetics. And the interaction of the calcium source and the porous carbon skeleton improves the stability of the adsorbent, and the crystallinity and the morphology are basically unchanged after ten times of cyclic tests.
The invention also provides the MOFs derivative porous adsorbent anchored by the calcium chloride clusters and prepared by the preparation method.
The adsorption capacity of the MOFs derivative porous adsorbent anchored by the calcium chloride clusters is greatly improved, the water adsorption capacity under the low-humidity environment is greatly enhanced, and the air water collection in arid areas such as deserts and the like is facilitated. The MOFs derivative porous adsorbent anchored by the calcium chloride clusters has excellent photo-thermal performance, can be quickly heated to a higher temperature under illumination, can realize rapid solar-driven atmospheric water collection, has rapid desorption kinetics, can realize repeated adsorption and desorption cycles in one day, and improves daily water yield.
The invention also provides application of the calcium chloride cluster anchored MOFs derivative porous adsorbent in atmospheric water collection.
Preferably, the atmospheric humidity is 10-100%.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method adopts proper pyrolysis temperature, and can not completely destroy the crystal structure of the original Ca-MOF; meanwhile, a large amount of porosity of the original Ca-MOF is reserved, the pore volume is increased, and a large amount of pore space is provided for the subsequent in-situ formation of calcium chloride clusters. In addition, through the pyrolysis process, the photo-thermal performance of the adsorbent is improved, and the possibility is provided for realizing solar-driven atmosphere water collection subsequently.
(2) The preparation method adopts proper HCl steam treatment time to convert Ca-MOF into calcium chloride cluster anchored porous adsorbent in situ. Unlike traditional composite salt preparing process, the process has strong interaction between Cl ion and calcium ion in carbon skeleton to form homogeneously dispersed calcium chloride cluster rather than crystal, and this can prevent salt leakage and agglomeration and raise the adsorption capacity, especially the adsorption capacity in low humidity range and adsorption kinetics.
(3) The metal organic framework derivative porous adsorbent prepared by the invention has high adsorption capacity, rapid adsorption and desorption kinetics and excellent photo-thermal performance, and is expected to be used for actual atmospheric water collection. Indoor water collection experiments show that the adsorbent can be used in various humidity environments (low, medium and high humidity), and outdoor water collection experiments show that the adsorbent has good adsorption capacity under typical drought climates, and has important significance for solving the problem of lack of fresh water in arid areas such as deserts and the like.
Drawings
FIG. 1 is a scanning electron microscope picture of Ca-MOF prepared in comparative example 1; wherein, (a) the scale is 10 μm and (b) the scale is 200nm;
FIG. 2 is an X-ray diffraction pattern of the calcium-containing porous carbon PC prepared in comparative examples 2-4;
FIG. 3 is a scanning electron microscope picture of the calcium-containing porous carbon PC prepared in comparative examples 2-4; wherein, (a) and (b) are PC-4, and the scales are 20 μm and 2 μm respectively; (c) and (d) are PC-51, and the scales are 20 μm and 2 μm respectively; (e) and (f) are PC-52, and the scales are 20 μm and 2 μm respectively;
FIG. 4 is a Raman spectrum of the calcium-containing porous carbon PC prepared in comparative examples 2-4;
FIG. 5 is an X-ray diffraction pattern of the adsorbent PCC prepared in examples 1-4;
FIG. 6 is a scanning electron microscope image of the adsorbent PCC prepared in examples 1-4; wherein, (a) and (b) are PCC-41, and the scales are 20 μm and 2 μm respectively; (c) (d) PCC-42, scale bars 20 μm and 2 μm, respectively; (e) (f) PCC-51, scale bars 20 μm and 2 μm, respectively; (g) (h) PCC-52, scale bars 20 μm and 2 μm, respectively;
FIG. 7 is an infrared spectrum of the adsorbent PCC prepared in examples 1-4;
FIG. 8 is an X-ray photoelectron spectrum picture of the adsorbent PCC prepared in examples 1-4;
FIG. 9 is a Raman spectrum of the adsorbent PCC prepared in examples 1-4;
FIG. 10 is an X-ray diffraction pattern of Ca-MOF, PC-4 and PCC-42 prepared in comparative examples 1,2 and example 2;
FIG. 11 is an infrared spectrum of Ca-MOF, PC-4 and PCC-42 prepared in comparative examples 1,2 and example 2;
FIG. 12 is a high resolution transmission electron microscope (a), diffraction (b), high angle annular dark field (c) and energy spectrum scan (d-i) of PCC-42 prepared in example 2;
FIG. 13 is a graph showing nitrogen adsorption and desorption (a) and pore size distribution (b) of Ca-MOF, PC-4 and PCC-42 prepared in comparative examples 1,2 and example 2;
FIG. 14 is an absorption spectrum (a) and a photothermal temperature increase profile (b) of PCC-42 prepared in example 2;
FIG. 15 is a graph of water vapor adsorption curve (a), low humidity adsorption capacity histogram (b), static adsorption and desorption curve (c), water adsorption (d) and desorption rate (e) histogram and dehydration rate histogram (f) for Ca-MOF, caCl 2·2H2 O and PCC-42 prepared in comparative example 1 and example 2;
FIG. 16 is a water vapor adsorption curve of PCC-42-W prepared in comparative example 5;
FIG. 17 is a graph of static adsorption and desorption curves (a) - (c), a low humidity adsorption capacity histogram (d), a dehydration rate histogram (e) and a water vapor adsorption curve (f) for PCC-41, PCC-51 and PCC-52 prepared in examples 1,3 and 4;
FIG. 18 is a graph comparing the performance of PCC-42 prepared in example 2 with that of MOFs adsorbents reported in the literature; wherein, (a) is adsorption capacity and (b) is water adsorption rate;
FIG. 19 is a photograph of a 26% RH water collection experiment of PCC-42 prepared in example 2 at 20℃indoors; wherein, (a) is an environmental temperature and humidity change curve, and (b) is an optical photograph of the surface of the water collector;
FIG. 20 is a photograph of a 45% RH water collection experiment of PCC-42 prepared in example 2 at 27℃indoors; wherein, (a) is an environmental temperature and humidity change curve, and (b) is an optical photograph of the surface of the water collector;
FIG. 21 is a photograph of an experiment of the PCC-42 prepared in example 2 with 85% RH water collection at 25℃indoors; wherein, (a) is an environmental temperature and humidity change curve, and (b) is an optical photograph of the surface of the water collector;
FIG. 22 is a graph showing the performance of PCC-42 prepared in example 2 in an outdoor water collection test and a cycle stability test; (a) The outdoor atmosphere is collected with water yield of each cycle and corresponding environmental temperature, humidity and illumination intensity change diagrams; (b) An optical picture of condensed water on the inner side surface of the water collector; (c) the concentration of each metal ion in the collected water; (d) The environment temperature and humidity change diagram corresponds to the circulation stability experiment; (e) The water absorption retention and the dehydration retention relative to the first cycle were tested for each cycle.
Detailed Description
Comparative example 1
Calcium chloride dihydrate (1.47 g) and 2, 5-bis (2H-tetrazol-5-yl) terephthalic acid (H 4 dtztp) (1.2 g) were weighed, added to a mixed solution containing acetonitrile/N, N' -Dimethylacetamide (DMA)/deionized water/concentrated hydrochloric acid (100 mL/400mL/100mL/5 mL), dispersed ultrasonically for 10 minutes, then transferred to an oven preheated at 115℃for heating for 72 hours, then washed three times with ethanol and methanol, respectively, and finally dried at 60℃for 12 hours to obtain Ca-MOF.
FIG. 1 is an SEM image of Ca-MOF obtained in comparative example 1, the Ca-MOF having a block structure, a smoother surface and a large number of micropores.
Comparative examples 2 to 4
The Ca-MOF prepared in comparative example 1 was placed in a tube furnace under nitrogen atmosphere and heated to the following temperatures at heating rates of 10℃min -1:
Comparative example 2: preserving heat for 5h at 400 ℃, and then cooling to room temperature along with a furnace to obtain calcium-containing porous carbon PC-4;
comparative example 3: keeping the temperature at 500 ℃ for 5 hours, and recording the obtained calcium-containing porous carbon as PC-51;
Comparative example 4: the temperature is kept at 500 ℃ for 24 hours, and the obtained calcium-containing porous carbon is marked as PC-52.
Figure 2 is an XRD image of samples obtained at different pyrolysis temperatures and pyrolysis times. When the pyrolysis temperature is 400 ℃ and the temperature is kept for 5 hours, only one wider diffraction peak appears in the obtained PC-4; as the pyrolysis temperature and time increases, the diffraction peak of the corresponding calcium carbonate increases. Fig. 3 is an SEM image of the corresponding calcium-containing porous carbon. It can be seen that a large number of pores were created in the different samples after pyrolysis, with a large change in morphology from the original Ca-MOF, wherein the PC-52 sample indicated the presence of a large number of small particles, which was associated with a large production of calcium carbonate. Fig. 4 shows raman spectra of the corresponding calcium-containing porous carbon, and it can be seen that the defect ratio in the structure gradually decreases with increasing pyrolysis temperature or time, which is related to the increase in the content of calcium carbonate produced as described above. Since we want to obtain uniformly distributed calcium chloride clusters on the nanometer scale, we choose the optimum pyrolysis temperature and time to be 400 ℃,5h, denoted as PC-4.
Examples 1 and 2
And (3) placing the prepared Ca-MOF in a tube furnace in a nitrogen atmosphere, heating to 400 ℃ at a heating rate of 10 ℃ min -1, preserving heat for 5 hours, and then cooling to room temperature along with the furnace to obtain the calcium-containing porous carbon PC-4. Subsequently, 30mg of porous carbon PC-4 was sealed in a container containing 20mL of concentrated hydrogen chloride solution (HCl), taking care that calcium-containing porous carbon PC-4 was not directly contacted with the HCl solution, and after steaming for 12 (example 1) or 24 hours (example 2), it was dried at 120℃for 12 hours, and the obtained sample was designated as PCC-41 or PCC-42.
Example 3
And (3) placing the prepared Ca-MOF in a tube furnace in a nitrogen atmosphere, heating to 500 ℃ at a heating rate of 10 ℃ min -1, preserving heat for 5 hours, and then cooling to room temperature along with the furnace to obtain the calcium-containing porous carbon PC-51. Subsequently, 30mg of porous carbon PC-51 was sealed in a container containing 20mL of a concentrated hydrogen chloride solution (HCl), taking care that calcium-containing porous carbon PC-51 was not directly contacted with the HCl solution, and after steaming for 24 hours, it was dried at 120℃for 12 hours, and the obtained sample was designated as PCC-51.
Example 4
And (3) placing the prepared Ca-MOF in a tube furnace in a nitrogen atmosphere, heating to 500 ℃ at a heating rate of 10 ℃ min -1, preserving heat for 24 hours, and then cooling to room temperature along with the furnace to obtain the calcium-containing porous carbon PC-52. Subsequently, 30mg of calcium-containing porous carbon PC-52 was sealed in a container containing 20mL of concentrated hydrogen chloride solution (HCl), and it was noted that porous carbon PC-52 was not directly contacted with HCl solution, and after steaming for 24 hours, it was dried at 120℃for 12 hours, and the obtained sample was designated as PCC-52.
FIGS. 5-9 are XRD, SEM, FTIR, XPS and Raman images of the adsorbents obtained in examples 1-4, respectively. Wherein, the pyrolysis condition is 400 ℃ and the sample for 5 hours still keeps a wider carbon diffraction peak after being subjected to HCl steam treatment time of 12-24 hours, and no crystallization peak of calcium chloride dihydrate is generated; however, the corresponding calcium carbonate diffraction peak disappeared after HCl vapor treatment of the sample under other pyrolysis conditions, and a new diffraction peak of calcium chloride dihydrate appeared. SEM images show that the morphology of the adsorbent is not changed basically after HCl steam treatment; FTIR spectra showed that the corresponding Ca-MOF ligand vibration disappeared after HCl steaming, indicating that Cl ions have a strong interaction with Ca in the porous carbon. The intensity of each element corresponding to XPS varies with HCl steaming time as shown in Table 1. Raman spectroscopy indicated that defects in the structure were reduced after HCl steaming, which was associated with the formation of calcium chloride clusters or calcium chloride dihydrate.
TABLE 1
Comparative example 5
And (3) placing the prepared Ca-MOF in a tube furnace in a nitrogen atmosphere, heating to 400 ℃ at a heating rate of 10 ℃ min -1, preserving heat for 5 hours, and then cooling to room temperature along with the furnace to obtain the calcium-containing porous carbon PC-4. Subsequently, 30mg of porous carbon PC-4 was sealed in a container containing 20mL of concentrated hydrogen chloride solution (HCl), taking care that calcium-containing porous carbon PC-4 was not directly contacted with the HCl solution, and after steaming for 24 hours, it was dried at 120℃for 12 hours, and the obtained sample was designated as PCC-42. Subsequently, the calcium chloride clusters in PCC-42 were washed with deionized water multiple times and dried to give a pure porous carbon adsorbent, designated PCC-42-W.
Fig. 10, 11 are XRD and FTIR images of comparative examples 1,2 and example 2. Ca-MOF showed higher crystallinity, consistent with the literature. After pyrolysis at 400 ℃, a broad carbon diffraction peak is obtained, and in the corresponding FTIR spectrum, the vibration of COO-corresponding to the ligand is reduced, indicating that part of bonds are broken after pyrolysis. When HCl is steam treated, no obvious calcium chloride hydrate crystallization peak appears, which indicates that calcium chloride exists in a cluster rather than a crystal form, and the vibration of the corresponding ligand completely disappears, which indicates that the interaction between Cl and Ca is strong. High resolution electron microscope characterization of PCC-42, as shown in FIG. 12, showed no apparent lattice fringes and no brighter calcium chloride particles in the HAADF image when the resolution was 10nm, and the corresponding elemental mapping image showed uniform C/N/O/Ca/Cl dispersion, further demonstrating that calcium chloride cluster anchored porous adsorbents could be obtained in situ by the HCl steaming process.
Fig. 13 is a nitrogen adsorption-desorption curve and a pore size distribution curve of comparative examples 1,2 and example 2. Ca-MOF shows a type I adsorption curve with a pore size distribution of 0.5-1nm, corresponding to BET and pore volume of 1010m 2 g-1and 0.41cm3 g-1. PC-4 and PCC-42 samples exhibited type III isotherms with lower BET, 47m 2 g-1 and 25m 2 g-1, respectively, which are associated with the formation of many macropores after pyrolysis. In addition, PC-4 and PCC-42 retain the micropores of the Ca-MOF, indicating that pyrolysis and subsequent HCl vapor etching processes do not completely destroy the porous structure of the MOF, and the resulting hierarchical porous structure facilitates heat and mass transfer and ultimately enhances adsorption kinetics. In contrast, the PCC-42-W prepared in comparative example 5 exhibited a specific surface area comparable to Ca-MOF (692 m 2 g-1) (Table 2), and in addition, its pore volume increased to 0.86cm 3 g-1, demonstrating that the pyrolysis and HCl etching processes favor enhanced porosity, and thus, the MOF-derived porous carbon provided a rich void space for anchoring CaCl 2 clusters.
TABLE 2
FIG. 14 is a graph showing the UV-vis-NIR absorption spectrum and the photothermal temperature increase change of example 2. It can be seen that PCC-42 has a high light absorption capacity (> 90%) in the wavelength range of 200-2500, and can rapidly rise from 32.6℃to 76℃in 2 minutes under light and reach equilibrium (82 ℃) after 10 minutes. This excellent photo-thermal response is attributed to the hierarchical porous structure of PCC-42, which can enhance multi-level reflection, extend the optical path, and ultimately enhance light absorption. Photo-thermal properties of PCC-42 at different light intensities were also evaluated. At 0.7, 1.5 and 2 sunlight illumination intensities, the surface temperature of PCC-42 can be respectively increased to 64.8, 95.2 and 105 ℃ within 10 minutes, and after the illumination is removed, the temperature of PCC-42 is rapidly reduced, so that the rapid photo-thermal response capability is further demonstrated.
Fig. 15 (a) compares the water adsorption properties of comparative example 1, example 2 and calcium chloride dihydrate. PCC-42 exhibits the highest water absorption capacity of 3.04g g -1, 8.7 times and 3.5 times the maximum absorption capacity of Ca-MOF (0.35 g g -1) and CaCl 2·2H2O(0.86g g-1, respectively. The increase in adsorption capacity in PCC-42 may be explained as follows: first, the MOF-derived porous carbon provides sufficient pore space for even distribution of CaCl 2 clusters in the structure. (based on ICP-OES results, the mass percent of CaCl 2 clusters in PCC-42 was as high as 49.8 wt.%). Secondly, the interaction of Ca and a carbon skeleton is also beneficial to anchoring of CaCl 2 clusters, so that the problem of salt leakage is effectively prevented. In addition, caCl 2 clusters formed in situ are used as main adsorption sites which are fully contacted with water molecules, so that the overall adsorption capacity is improved. The pure porous carbon skeleton (PCC-42-W) also plays a role in the increase of adsorption capacity, as shown in FIG. 16.
The comparison of the water adsorption capacities of the different samples at 20-50% RH is shown in FIG. 15 (b). Of all the adsorbents tested, PCC-42 had the highest water adsorption performance at 20%, 30%, 40% and 50% RH of 0.45, 0.59, 0.76 and 0.9g g -1, respectively. The water absorption capacity of PCC-42 is increased by 421%, 333%, 308% and 279% at 20-50% RH, respectively, as compared to Ca-MOF. Notably, the water absorption capacity of PCC-42 was increased by 940% and 351% at 20% and 30% RH, respectively, as compared to CaCl 2·2H2 O. In addition, PCC-42 exhibits rapid adsorption and desorption kinetics (FIGS. 15 (c) - (f)), achieving an equilibrium water adsorption of about 80-94% within 50 minutes, and releasing 75-86% of the adsorbed water within 50 minutes under a sun light. In addition, the calculated adsorption and desorption rates show that the performance of PCC-42 is far superior to that of Ca-MOF and CaCl 2·2H2 O. The water adsorption rates of PCC-42 at 20-50% RH were 0.4, 0.622, 0.875 and 1.01kg -1h-1, corresponding to 4.67, 4.8, 4.01 and 3.65 times Ca-MOF, respectively, and 21.7, 7.81, 2.7, 1.97 times CaCl 2·2H2 O. Furthermore, the desorption rate of PCC-42 with different water contents under one light irradiation is about 2.6-15.4 times that of Ca-MOF and CaCl 2·2H2 O. Typically, the adsorption process of CaCl 2 involves chemisorption, hydration and solution absorption, but the high regeneration temperature (> 250 ℃) of CaCl 2 limits its practical use. In contrast, PCC-42 adsorbents show a fast water release capacity (83%) within 1.5 hours under one irradiation of sunlight, whereas Ca-MOF and CaCl 2×2H2 O have desorption capacities of 39% and 47%, respectively, demonstrating that in situ preparation of CaCl 2 cluster anchored porous adsorbents can achieve more efficient solar driven water release with the advantages of no external energy input, environmental protection and sustainability. The water absorption and desorption properties corresponding to examples 1,3 and 4 are shown in FIG. 17. Because PCC-42 exhibits optimal adsorption capacity and rapid adsorption and desorption kinetics in a low humidity range over the same adsorption time, PCC-42 was selected as the optimal sample for subsequent indoor and outdoor water collection experiments.
FIG. 18 is a graph comparing the adsorption capacity and water adsorption rate of example 2 with other typical MOFs adsorbents. It can be seen that PCC-42 has excellent adsorption capacity and adsorption rate over various humidity ranges.
Fig. 19-21 are optical photographs of the corresponding environmental temperature and humidity profiles, and water collector surfaces, of example 2 during indoor water collection. The PCC-42 adsorbents have water adsorption, desorption and collection capacities of 0.36, 0.23 and 0.185g g -1, respectively, at 20-26% RH. In contrast, the water collection performance increases with increasing ambient humidity. The water absorption, dewatering and collection capacities of the PCC-42 adsorbent were 0.622, 0.45 and 0.4g g -1, respectively, at 27-45% RH. When the relative humidity is as high as 85%, the highest water collection capacity of the PPC-42 adsorbent is 1.386g g -1 (adsorption capacity: 1.89g g -1; desorption capacity: 1.46g g -1), and the problem of salt leakage does not exist. The results show that in our work, the PCC-42 adsorbent has good stability and wide application prospect, and can be used for solar energy driven atmosphere water collection under various humidity environments.
Figure 22 is a graph of example 2 water collection outdoors, where 1.13 liters of water per kilogram of adsorbent can be collected over a 7 hour period, which is higher than reported MOFs adsorbents driven only by sunlight in desert climates. The ion detection is carried out on the collected water quality through ICP-OES, the concentration of Ca 2+、K+、Mg2+ and Na + ions in the collected water is far lower than the drinking water standard (10 3 ppm) of the world health organization, and the practical application potential of PCC-42 in solving the problem of water shortage is demonstrated. Furthermore, we performed ten cycle tests. Although the adsorption capacity of PCC-42 fluctuates with changes in ambient humidity relative to the first cycle performance, the water release capacity remains close to 100%, indicating that PCC-42 adsorbent has excellent cycle stability.
The foregoing embodiments have described the technical solutions and advantages of the present invention in detail, and it should be understood that the foregoing embodiments are merely illustrative of the present invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like that fall within the principles of the present invention should be included in the scope of the invention.
Claims (8)
1. A method for preparing a calcium chloride cluster anchored MOFs-derived porous adsorbent, comprising the steps of:
(1) Placing Ca-MOF in inert gas atmosphere, pyrolyzing at 300-800 ℃ for 5-24h, and marking as calcium-containing porous carbon PC;
(2) And (3) treating the calcium-containing porous carbon PC with HCl steam for 5-24h, and drying to obtain the calcium chloride cluster anchored MOFs derivative porous adsorbent.
2. The method for preparing calcium chloride cluster anchored MOFs-derived porous adsorbent according to claim 1, wherein in step (1), the pyrolysis temperature is 300-500 ℃ and the pyrolysis time is 5-24h.
3. The method for preparing calcium chloride cluster anchored MOFs-derived porous adsorbent according to claim 1, wherein in step (2), HCl steaming time is 12-24h.
4. The method of preparing calcium chloride cluster anchored MOFs-derived porous adsorbents according to claim 1, wherein step (2) comprises: and (3) sealing the calcium-containing porous carbon PC in a container containing a concentrated hydrogen chloride solution, treating the calcium-containing porous carbon PC for 5-24 hours by adopting HCl steam, and drying to obtain the calcium chloride cluster anchored MOFs derivative porous adsorbent.
5. The method for preparing calcium chloride cluster anchored MOFs-derived porous adsorbent according to claim 4, wherein said concentrated hydrogen chloride solution has a mass concentration of 36-38%.
6. A metal organic framework-derived porous adsorbent prepared by the method of any one of claims 1 to 5, wherein the MOFs-derived porous adsorbent is anchored by calcium chloride clusters.
7. Use of the calcium chloride cluster anchored MOFs-derived porous adsorbent of claim 6 in atmospheric water collection.
8. Use according to claim 7, characterized in that the atmospheric humidity is 10-100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310445127.3A CN116550290B (en) | 2023-04-24 | 2023-04-24 | Calcium chloride cluster anchored MOFs derived porous adsorbent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310445127.3A CN116550290B (en) | 2023-04-24 | 2023-04-24 | Calcium chloride cluster anchored MOFs derived porous adsorbent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116550290A CN116550290A (en) | 2023-08-08 |
| CN116550290B true CN116550290B (en) | 2024-05-03 |
Family
ID=87499289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310445127.3A Active CN116550290B (en) | 2023-04-24 | 2023-04-24 | Calcium chloride cluster anchored MOFs derived porous adsorbent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116550290B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117563557B (en) * | 2023-11-03 | 2024-10-11 | 江苏海普功能材料有限公司 | Defluorination adsorbent, preparation method thereof and defluorination method of lithium battery recovery liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321815A (en) * | 2001-06-21 | 2001-11-14 | 上海交通大学 | Adsorption air water-intaking equipment |
| US9061235B1 (en) * | 2009-08-02 | 2015-06-23 | Eurica Califorrniaa | Method of collecting water on the moon |
| CN109056902A (en) * | 2018-08-20 | 2018-12-21 | 姜喜辉 | A kind of device and method thereof for extracting water from atmospheric air |
| CN114042436A (en) * | 2021-11-25 | 2022-02-15 | 北京化工大学 | Molded MOFs material and preparation method and application thereof |
| CN114369254A (en) * | 2021-12-27 | 2022-04-19 | 五邑大学 | Photochromic Ca-MOF material and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10640954B2 (en) * | 2016-12-20 | 2020-05-05 | Massachusetts Institute Of Technology | Sorption-based atmospheric water harvesting device |
| US12070734B2 (en) * | 2021-03-05 | 2024-08-27 | National University Of Singapore | Aerogel for harvesting atmospheric water |
-
2023
- 2023-04-24 CN CN202310445127.3A patent/CN116550290B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321815A (en) * | 2001-06-21 | 2001-11-14 | 上海交通大学 | Adsorption air water-intaking equipment |
| US9061235B1 (en) * | 2009-08-02 | 2015-06-23 | Eurica Califorrniaa | Method of collecting water on the moon |
| CN109056902A (en) * | 2018-08-20 | 2018-12-21 | 姜喜辉 | A kind of device and method thereof for extracting water from atmospheric air |
| CN114042436A (en) * | 2021-11-25 | 2022-02-15 | 北京化工大学 | Molded MOFs material and preparation method and application thereof |
| CN114369254A (en) * | 2021-12-27 | 2022-04-19 | 五邑大学 | Photochromic Ca-MOF material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116550290A (en) | 2023-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116550290B (en) | Calcium chloride cluster anchored MOFs derived porous adsorbent and preparation method and application thereof | |
| CN106964339B (en) | Carbon-doped ultrathin bismuth tungstate nanosheet photocatalytic material and preparation method thereof | |
| Hu et al. | CaCl2 Nanocrystals decorated photothermal Fe-ferrocene MOFs hollow microspheres for atmospheric water harvesting | |
| Cao et al. | Novel composite phase change materials based on hollow carbon nanospheres supporting fatty amines with high light-to-thermal transition efficiency | |
| Hu et al. | Metal-organic frameworks for solar-driven atmosphere water harvesting | |
| Wang et al. | Hexagonal cluster Mn-MOF nanoflowers with super-hydrophilic properties for efficient and continuous solar-driven clean water production | |
| US20040031387A1 (en) | Boron-oxide and related compounds for hydrogen storage | |
| CN109911880B (en) | Method for preparing nitrogen-containing carbon aerogel through normal-pressure drying in super-salt environment | |
| Hu et al. | MOF supraparticles for atmosphere water harvesting at low humidity | |
| CN110756223A (en) | Adsorption catalysis composite material and application thereof in pollutant treatment | |
| Luo et al. | Bimetallic MOF‐Derived Solar‐Triggered Monolithic Adsorbent for Enhanced Atmospheric Water Harvesting | |
| CN112827470A (en) | Selective air water-absorbing MOFs material with high stability and preparation method thereof | |
| Wang et al. | High‐performance and wide relative humidity passive evaporative cooling utilizing atmospheric water | |
| CN114247432B (en) | Carbon fiber loaded MOF material, preparation method and air water collecting device | |
| Zhang et al. | Autonomous Atmospheric Water Harvesting over a Wide RH Range Enabled by Super Hygroscopic Composite Aerogels | |
| He et al. | A Hybrid Photocatalytic System Splits Atmospheric Water to Produce Hydrogen | |
| CN113774429A (en) | ZIF-8/graphene composite aerogel and preparation method and application thereof | |
| Luo et al. | Symbiotic Defect-reinforced Bimetallic MOF-derived Fiber Components for Solar-assisted Atmospheric Water Collection | |
| Zhang et al. | Atmospheric water extraction–a review from materials to devices | |
| CN114471620B (en) | alpha-SnWO 4 /In 2 S 3 Composite photocatalyst | |
| Xu et al. | Study on the adsorption of Ce (III) on phosphonic acid functionalized ZIF-67@ SiO2 magnetic porous carbon materials | |
| CN113634244B (en) | High-index crystal face GO@Cd rich in sulfur vacancies 1-x Zn x S polyhedral material and preparation method thereof | |
| CN115634660A (en) | Photo-thermal driving air water-collecting composite material, and preparation method and application thereof | |
| CN111617806B (en) | g-C with sodium citrate as matrix 3 N 4 MOFs composite photocatalytic material and preparation method and application thereof | |
| CN108786733B (en) | Nano-pore carbon sphere CO with micron scale2Method for preparing adsorbent |
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 |