CN108408871A - A kind of novel environmental persistent free radicals material and preparation method thereof - Google Patents
A kind of novel environmental persistent free radicals material and preparation method thereof Download PDFInfo
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- CN108408871A CN108408871A CN201810211958.3A CN201810211958A CN108408871A CN 108408871 A CN108408871 A CN 108408871A CN 201810211958 A CN201810211958 A CN 201810211958A CN 108408871 A CN108408871 A CN 108408871A
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- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000007613 environmental effect Effects 0.000 title claims abstract description 13
- 230000002085 persistent effect Effects 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 38
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 38
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 38
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 38
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000005751 Copper oxide Substances 0.000 claims abstract 2
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 15
- 238000000197 pyrolysis Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 5
- 238000011835 investigation Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001802 infusion Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005364 hyperfine coupling Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to organic/inorganic composite material technical field, it is related to a kind of novel environmental persistent free radicals material and preparation method thereof.The material is pyrolyzed by the temperature condition lower limit oxygen at 400 DEG C, makes to be supported on matrix copper oxide CuO/ silica SiO2Catechol CT Partial Conversions on surface obtain EPFRs, wherein CT and matrix CuO/SiO2Mass ratio is that 0.032, EPFRs grain sizes are not more than 100 μm, and the g factors are more than 2.0040, and spin concentration is in 0.5*1016spins·L‑1~1.5*1016spins·L‑1Between.Steps are as follows for the preparation method of the present invention：(1)CuO/SiO2The preparation of matrix；(2) preparation of EPFRs.This method have it is easy to operate, be easy to control, it is of low cost the advantages that.The material obtained by this method can be applied in the degradation of some organic pollutants.
Description
Technical field
The invention belongs to composite organic-inorganic material technical fields, are related to a kind of novel environmental persistent free radicals material
And preparation method thereof.
Background technology
In recent years, environmental persistence free radical EPFRs shows certain superiority in terms of promoting contaminant degradation.
In water environment, EPFRs can generate active oxygen species (ROS, such as：·OH、O2 ·-、H2O2), H can be activated2O2OH is generated,
And activation persulfate generates SO4 ·-, to achieve the purpose that contamination-free of degrading.Using DMPO as spin traps knot
DPMO and its respective addition compound product can be detected by closing EPR spectrum.It is generally acknowledged that the particle that EPFRs is generated in imperfect combustion
It is generated on object and on contaminated soil particle more.The side mainly loaded at present with gas phase for the laboratory preparation method of EPFRs
Based on formula, the research that EPFRs is prepared using organic matter infusion process is rarely reported.More stringent control is needed compared to gas phase load
The limitations such as condition processed and the higher pressure of instrument, temperature capacity prepare EPFRs with easy to operate easy using infusion process
The advantages that row, data stabilization be reliable, economical and effective, the expansion for laboratory research of being more convenient for.
Invention content
The present invention discloses a kind of novel environmental persistent free radicals material and preparation method thereof, it is therefore an objective to provide a kind of operation
Simple and practicable, the cost-effective free sill of environmental persistence.
Technical scheme is as follows：
A kind of novel environmental persistent free radicals material is supported on matrix oxygen under 400 DEG C of temperature conditions by limiting oxygen pyrolysis
Change copper CuO/ silica SiO2Catechol CT on surface makes its Partial Conversion that EPFRs be made, wherein CT and matrix CuO/
SiO2Mass ratio is that 0.032, EPFRs grain sizes are not more than 100 μm, and the g factors are more than 2.0040, and spin concentration is in 0.5*
1016spins·L-1~1.5*1016spins·L-1Between.
A kind of preparation method of novel environmental persistent free radicals material, is as follows：
(1)CuO/SiO2The preparation of matrix：Prepare the Cu (NO of 0.05~1.0mM3)2Methanol solution；It is added to particle
SiO2In, Cu (NO3)2Solution and SiO2Volume mass proportioning be 10ml：1g, ultrasonic deoxidation processing；It stirs evenly, in room temperature
Lower adsorption equilibrium；It first dries, then calcines 3h under 450 DEG C of temperature conditions, then Temperature fall；After being cooled to room temperature, it is made
CuO/SiO2Blapharoplast；
(2) preparation of EPFRs：The methanol solution of catechol CT is added to the CuO/SiO obtained in step (1)2Base
In body particle, CT and CuO/SiO is controlled2The mass ratio of matrix is 0.032；It stirs evenly and is placed on shaking table concussion, fully react
Afterwards, the blapharoplast that surface is rich in CT is obtained；It is dry, tinfoil paper sealing, closed system is pyrolyzed 2h at 400 DEG C, makes catechol CT
It is converted to the EPFRs of surface combination.
Beneficial effects of the present invention：The invention passes through Oxygen Condition, pyrolysis temperature, CT/SiO2Mass ratio, metal oxide
Closed system (limit oxygen), medium temperature, high CT/SiO are selected in the investigation of the control conditions such as concentration2The condition of mass ratio, high CuO concentration
Realize the preparation of high concentration EPFRs.The preparation method provides a set of simple as the preparation for being combined as EPFRs of conventional method
Feasible, economical and practical and reliable and stable method.The material obtained by this method can be applied to the drop of certain organic pollutions
Xie Zhong.
Description of the drawings
Fig. 1 is the process flow chart of the present invention；
Fig. 2 (a) is CuO/SiO prepared by SEM-EDS analyses under the conditions of 5.00 μm2Basis material schematic diagram；
Fig. 2 (b) is CuO/SiO prepared by SEM-EDS analyses under the conditions of 4.00 μm2Basis material schematic diagram；
Fig. 2 (c) is CuO/SiO prepared by SEM-EDS analyses under the conditions of 3.00 μm2Basis material schematic diagram；
Fig. 3 is CuO/SiO2Basis material granularmetric analysis figure；
Fig. 4 is CuO/SiO prepared by EPR analyses2Basis material schematic diagram；
Under the conditions of Fig. 5 (a) is open system, EPR analyzes Oxygen Condition for system (CT-CuO/SiO2) in EPFRs
Influence schematic diagram；
Under the conditions of Fig. 5 (b) is closed system, EPR analyzes Oxygen Condition for system (CT-CuO/SiO2) in EPFRs
Influence schematic diagram；
Fig. 6 is that EPR analyzes pyrolysis temperature to closed system (CT-SiO2) in EPFRs generate influence schematic diagram；
Fig. 7 is EPR analyses CT/SiO2Mass ratio is to closed system (CT-SiO2) in EPFRs generate influence schematic diagram；
Fig. 8 is that EPR analyzes CuO concentration to closed system (CT-CuO/SiO2) in EPFRs generate influence and CuO/
SiO2Necessity schematic diagram prepared by basis material.
Specific implementation mode
Below in conjunction with attached drawing and technical solution, the specific implementation mode that further illustrates the present invention.
SiO2It is the common inorganic material of laboratory simulation burning, is often used as inert material control transiting metal oxidation
Object concentration.In the present invention, with CuO/SiO2It was pyrolyzed using CT as pollutant presoma using infusion process research as matrix
The generation of EPFRs on journey particulate matter.
A kind of preparation method of novel environmental persistent free radicals material, technological process are as shown in Fig. 1.
(1) CuO/SiO first before the preparation for carrying out EPFRs2Prepared by basis material, the CuO/SiO of preparation2SEM-
EDS material morphologies are as shown in Fig. 2；Particle diameter distribution is as shown in Fig. 3, and grain size is not more than 100 μm.Concrete operations are：It is accurate to claim
Take Cu (NO3)2·3H2O is added in 40mL methanol, is made into the Cu (NO that concentration range is 0.05~1.0mM3)2Methanol solution；It is super
Sound deoxidation processing 10min；Respectively it is added to 4.0g SiO2In, it stirs evenly, at room temperature adsorption equilibrium 48h；105 DEG C of constant temperature are dry
After dry, 3h is pyrolyzed at 450 DEG C, temperature program is set as：60min is warming up to 450 DEG C, maintains 450 DEG C of 3h, then drops naturally
Temperature.It is taken out to get to CuO/SiO after being cooled to room temperature2Basis material.
(2) EPR is used to analyze CuO/SiO2Basis material, spectrogram are as shown in Fig. 4.SiO2The Cu on surface shows one kind
Non- mean value Cu signals, its parallel zone have four lines, are formed by Cu (II) S=1/2 and nuclear spin I=3/2 hyperfine couplings.
Wave spectrum shows that the center Cu (II) is axial, g//>g⊥>2.0.For transition metal ions, spin-orbit even summation is made
It is very wide so as to cause spectral line with generally very strong.EPR test method concrete operations are：25.00mg EPFRs particles accurately are weighed,
It is put in the high-purity quartz tube of 4mm internal diameters, in progress EPR tests under room temperature.EPR parameter settings are：Microwave frequency
9.43GHz, microwave power 10mW, central magnetic field 3360G, sweep length 100G, modulating frequency 100kHz, reception gain 1.0*
103, sweep time 61.44s, 1024 points of resolution ratio, scanning 1 time.
(3) investigation of Oxygen Condition is carried out, analysis Oxygen Condition is for system (CT-CuO/SiO2) in EPFRs generate
It influences, as a result as shown in Fig. 5.The EPFRs signal strengths prepared under limited oxygen condition it can be seen from Fig. 5 are apparently higher than not
Limit oxygen pyrolysis.Concrete operations are：Weigh the matrix that 2.0g is prepared, be added to 20.0ml methanol preparation CT solution in, CT with
Matrix CuO/SiO2Mass ratio is chosen for 0.008；It stirs evenly, shake 3d with the rate of 150r/min obtains fully after reaction
Surface is rich in the blapharoplast of CT；And 55 DEG C of freeze-day with constant temperature in baking oven；Dried sample is placed in 25ml crucibles, tinfoil paper
Paper multilayer is sealed；Then open respectively in Muffle furnace (limit oxygen) and closing (unlimited oxygen) system pyrolysis.Limited oxygen condition is initial
It is continually fed into nitrogen, until oxygen closes air inlet/outlet after all driving out of.Limited oxygen condition is not that air inlet/outlet is opened, and keeps air
Convection current.Temperature program is set as：60min is warming up to 300 DEG C, heats 2h, then Temperature fall, makes catechol CT be converted to table
The EPFRs that face combines.
(4) investigation of pyrolysis temperature is carried out, analysis pyrolysis temperature is to closed system (CT-SiO2) in EPFRs generate shadow
It rings, as a result as shown in Fig. 6.As seen from Figure 6, EPFRs generates concentration highest when pyrolysis temperature is 400 DEG C, is 0.5*
1016spins·L-1, the g factors are 2.0043.The same embodiment of concrete operations (3), difference are：In this experiment, directly adopt
Use SiO2As basis material, matrix preparation time is reduced；Increase CT and matrix SiO simultaneously2Mass ratio is increased to from 0.008
0.032, to improve the production quantity of EPFR；It is pyrolyzed using the sealing condition that optimization obtains in embodiment (3)；Pyrolysis temperature
Test scope is 300~600 DEG C.
(5) CT/SiO is carried out2CT/SiO is analyzed in the investigation of mass ratio2Mass ratio is to closed system (CT-SiO2) in EPFRs
The influence of generation, as a result as shown in Fig. 7.As seen from Figure 7, CT/SiO2EPFRs generates concentration when mass ratio is 0.032
Highest is 0.5*1016spins·L-1, the g factors are 2.0043.The same embodiment of concrete operations (3), difference are：This reality
In testing, SiO is directly used2As basis material, matrix preparation time is reduced；Using the envelope that optimization obtains in embodiment (3)
The condition of closing is pyrolyzed；Pyrolysis temperature is using 400 DEG C of temperature of optimization in embodiment (4)；CT/SiO2Quality is than test scope
0.004~0.048.
(6) it carries out CuO concentration and Cu ion concentrations in matrix to investigate, analysis CuO concentration is to closed system (CT-CuO/
SiO2) in EPFRs generate influence and CuO/SiO2Necessity prepared by basis material.As a result as shown in Fig. 8.By in Fig. 8
As can be seen that the presence of CuO can promote SiO2The generation of surface EPFRs, and the life of the increase EPFRs with CuO concentration
It is continuously increased at concentration.And without CuO/SiO2The preparation of basis material loads, then while directly carrying out Cu ions with CT
Pyrogenous origin EPFRs concentration can be made to be substantially reduced, and constantly reduced with the increase EPFRs concentration of Cu ion concentrations.Therefore
CuO/SiO2The preparation of matrix is very necessary for preparing for EPFRs.Free radical maximum concentration can reach 1.5*
1016spins·L-1.The same embodiment of concrete operations (1) and (3), the difference is that：Using optimizing in embodiment (3)
To sealing condition be pyrolyzed；Pyrolysis temperature is using 400 DEG C of temperature of optimization in embodiment (4)；CT/ substrate quality ratios use
The mass ratio 0.032 optimized in embodiment (5)；When Cu ionic conditions are investigated, Cu (NO3)2·3H2O and CT is using specific implementation
(3) mode loads simultaneously in, and without step in specific implementation (1), CuO/SiO is proved to compare2Prepared by basis material must
The property wanted.
(7) it is obtained by Optimal Experimental：Under sealing condition, it is 400 DEG C to be pyrolyzed, CT/SiO2Mass ratio is 0.032, matrix
CuO/SiO2The EPFRs of maximum concentration can be prepared when a concentration of 1.0mM.
Claims (2)
1. a kind of novel environmental persistent free radicals material, which is characterized in that the novel environmental persistent free radicals material
It is to be supported on matrix copper oxide CuO/ silica SiO by limiting oxygen pyrolysis under 400 DEG C of temperature conditions2Catechol on surface
EPFRs is prepared in CT：CT and matrix CuO/SiO2Mass ratio is that 0.032, EPFRs grain sizes are not more than 100 μm, and the g factors are more than
2.0040 spin concentration is in 0.5*1016spins·L-1~1.5*1016spins·L-1Between.
2. a kind of preparation method of novel environmental persistent free radicals material, which is characterized in that steps are as follows：
(1)CuO/SiO2The preparation of matrix：Prepare the Cu (NO of 0.05~1.0mM3)2Methanol solution；It is added to particle SiO2In,
Cu(NO3)2Solution and SiO2Volume mass proportioning be 10ml：1g, ultrasonic deoxidation processing；It stirs evenly, absorption is flat at room temperature
Weighing apparatus；It first dries, then calcines 3h under 450 DEG C of temperature conditions, then Temperature fall；After being cooled to room temperature, CuO/SiO is made2Base
Body particle；
(2) preparation of EPFRs：The methanol solution of catechol CT is added to the CuO/SiO obtained in step (1)2Blapharoplast
In, control CT and CuO/SiO2The mass ratio of matrix is 0.032；Stir evenly be placed on shaking table concussion, fully reaction after, obtain
Surface is rich in the blapharoplast of CT；It is dry, tinfoil paper sealing, closed system is pyrolyzed 2h at 400 DEG C, and catechol CT is made to be converted to
The EPFRs that surface combines.
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| CN201810211958.3A CN108408871A (en) | 2018-03-08 | 2018-03-08 | A kind of novel environmental persistent free radicals material and preparation method thereof |
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| CN201810211958.3A CN108408871A (en) | 2018-03-08 | 2018-03-08 | A kind of novel environmental persistent free radicals material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607740A (en) * | 2018-12-19 | 2019-04-12 | 大连理工大学 | A kind of biological carbon materials of the free radical containing environmental persistence and preparation method thereof |
| CN113610326A (en) * | 2021-09-09 | 2021-11-05 | 中国科学院生态环境研究中心 | Method for predicting environmentally persistent radical generation performance |
| CN115739087A (en) * | 2022-11-10 | 2023-03-07 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Method for realizing persistent free radical regeneration of novel metal biochar composite catalyst and application |
| CN115956566A (en) * | 2022-12-23 | 2023-04-14 | 中国科学院生态环境研究中心 | Persistent free-radical material and preparation method and application thereof |
-
2018
- 2018-03-08 CN CN201810211958.3A patent/CN108408871A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607740A (en) * | 2018-12-19 | 2019-04-12 | 大连理工大学 | A kind of biological carbon materials of the free radical containing environmental persistence and preparation method thereof |
| CN113610326A (en) * | 2021-09-09 | 2021-11-05 | 中国科学院生态环境研究中心 | Method for predicting environmentally persistent radical generation performance |
| CN113610326B (en) * | 2021-09-09 | 2023-05-12 | 中国科学院生态环境研究中心 | Method for predicting environmental persistent radical generation performance |
| CN115739087A (en) * | 2022-11-10 | 2023-03-07 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Method for realizing persistent free radical regeneration of novel metal biochar composite catalyst and application |
| CN115739087B (en) * | 2022-11-10 | 2024-03-08 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Method for realizing regeneration of persistent free radicals by novel metal biochar composite catalyst and application |
| CN115956566A (en) * | 2022-12-23 | 2023-04-14 | 中国科学院生态环境研究中心 | Persistent free-radical material and preparation method and application thereof |
| WO2024130757A1 (en) * | 2022-12-23 | 2024-06-27 | 中国科学院生态环境研究中心 | Persistent free radical material, and preparation method therefor and use thereof |
| CN115956566B (en) * | 2022-12-23 | 2024-09-06 | 中国科学院生态环境研究中心 | Durable free-base material and preparation method and application thereof |
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Application publication date: 20180817 |