CN110479224A - Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application - Google Patents
Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application Download PDFInfo
- Publication number
- CN110479224A CN110479224A CN201910698044.9A CN201910698044A CN110479224A CN 110479224 A CN110479224 A CN 110479224A CN 201910698044 A CN201910698044 A CN 201910698044A CN 110479224 A CN110479224 A CN 110479224A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nitrogen carbon
- carbon nanomaterial
- solution
- preparation
- 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.)
- Pending
Links
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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to cobalt derived from a kind of organic metal framework/nitrogen carbon nanomaterials and its preparation method and application, the specific steps are as follows: (1) stirring and dissolving Co (NO in methyl alcohol3)2·6H2Co (NO is made in O3)2Solution；2-methylimidazole solution is made in stirring and dissolving 2-methylimidazole in methyl alcohol；To Co (NO3)22-methylimidazole solution is poured into solution, is stood aging, centrifugation, washing, drying at room temperature, is obtained ZIF-67；(2) step (1) is obtained ZIF-67 to make annealing treatment, obtains cobalt/nitrogen carbon nanomaterial after pickling, washing, drying.Compared with prior art, cobalt prepared by the present invention/nitrogen carbon material has the advantages such as metal dissolving is low, reusing is good, operating process is easy, pH is applied widely for activating peroxydisulfate, extensive in hardly degraded organic substance field of waste water treatment application prospect.
Description
Technical field
The present invention relates to catalyst fields, more particularly, to a kind of cobalt derived from organic metal framework/nitrogen carbon nanomaterial
And its preparation method and application.
Background technique
In recent years, the high-level oxidation technology based on persulfate (PS) priming reaction just becomes the removal difficulty drop to attract most attention
Solve one of the method for organic matter.Compared to hydroxyl radical free radical, the potentiometric titrations that persulfate generates possess higher oxidation
Reduction potential (2.5-3.1V), longer half-life period (≤30-40 μ s) and to the lower dependence of pH, therefore persulfate by
Gradually become a kind of novel advanced oxidation oxidant.Compared to other oxidants such as H2O2And O3Deng persulfate possesses high dissolution
Property, high redox potential, the advantages such as retention time is long in the environment, environmentally friendly and pH is applied widely.PS can be with
It is activated by modes such as heating, ultraviolet lighting and catalyst.Wherein compared to homogeneous metal ion catalyst, transition metal is urged
Agent, which activates PS, has secondary pollution low and the advantages such as contaminant removal efficiency is high, thus has received widespread attention.
In numerous catalyst, cobalt-based material is considered having preferable activation capacity to persulfate, just extensive at present
Research.Specific surface area and active site play an important role for the catalytic activity in heterogeneous interfacial reaction.However it is traditional
Cobalt/cobalt oxide is because specific surface area is smaller and being easy to the features such as reuniting during the reaction causes its catalytic activity to gradually decrease.
Although problem above can be improved by the way that cobalt nano material to be anchored in support materials, nano particle and solution it is direct
Contact can still result in Co2+Dissolution.Therefore, design has high activity and environmental-friendly cobalt-base catalyst is still necessary.
Currently, the hollow cavity structure nano material wrapped up by porous shell is got the attention.Wherein by cobalt/cobalt oxide
It is encapsulated into hollow nanostructures and forms unique nucleocapsid structure and can solve the above problem.But its preparation process complexity is simultaneously
And nanostructure is difficult to control.The magnetic metal cobalt nanocatalyst preparation being packaged in nitrogen doped carbon nanotube is convenient, but its
Specific surface area, cobalt content and degree of scatter are poor.Organic metal framework material (MOFs), can as a kind of porous catalyst material
Using the ideal shell as cobalt-base catalyst.But the MOFs material reported at present, such as Co-BTC there are stability difference and
It is difficult to the defects of being separated from the water.It is then lacked by the derivative nitride of MOF that a step is pyrolyzed Prussian blue similar object (PBAs) preparation
The research of weary carbon and nitrogen in catalytic activity especially in terms of PS catalytic activity.Currently, cobalt derived from ZIF-67/nitrogen carbon nanometer material
Material activation PS degradation of organic substances lacks relevant report.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of organic metal frameworks
Derivative cobalt/nitrogen carbon nanomaterial and its preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
Cobalt/nitrogen carbon nanomaterial preparation method derived from a kind of organic metal framework, the specific steps are as follows:
(1) preparation of Co/NC nano material presoma organometallic skeletal ZIF-67: stirring and dissolving Co in methyl alcohol
(NO3)2·6H2Co (NO is made in O3)2Solution；2-methylimidazole solution is made in stirring and dissolving 2-methylimidazole in methyl alcohol；To Co
(NO3)22-methylimidazole solution is poured into solution, is stood aging, centrifugation, washing, drying at room temperature, is obtained ZIF-67；
(2) step (1) cobalt derived from metal organic framework ZIF-67/nitrogen carbon nanomaterial preparation: is obtained into ZIF-67
It is made annealing treatment, obtains cobalt/nitrogen carbon nanomaterial after pickling, washing, drying.
Preferably, Co (NO in step (1)3)2Co (NO is added in every 250mL methanol for solution3)2·6H2The quality of O is
2.50g。
Preferably, 2-methylimidazole solution in step (1), 2-methylimidazole quality used in every 250mL methanol are
3.28g。
Preferably, in step (1): ageing time is that for 24 hours, drying temperature is 60 DEG C, drying time 12h.
Preferably, in step (2) the step of annealing are as follows: under argon atmosphere, 900 DEG C are warming up to 2 DEG C/min,
Maintain 3h.
Preferably, in step (2) the step of pickling are as follows: carry out pickling using the sulfuric acid solution of 0.5M, pickling time is
For 24 hours, excessive cobalt ions is removed, the catalyst dissolution of metal ion and problem of environmental pollution during the reaction are reduced.
A kind of derivative cobalt/nitrogen carbon nanomaterial of metal organic frame, using right any one of the above metal organic frame
What the preparation method of derivative cobalt/nitrogen carbon nanomaterial was prepared.
Preferably, the size of the Co/NC nano material is the nano particle of 300~400nm.
Cobalt/nitrogen carbon nanomaterial application derived from a kind of organic metal framework, it is useless for activating peroxydisulfate removal
Water pollutant, specific steps are as follows:
Cobalt/nitrogen carbon nanomaterial is added in waste water after mixing evenly, peroxydisulfate is added and is allowed to come into full contact with, stirs
It reacts, hardly degraded organic substance in water of degrading.
Preferably, the dosage of peroxydisulfate is 1~5mM, and cobalt/nitrogen carbon nanomaterial dosage is 25~200mg/
L, the pH of waste water are 5~9.
It is furthermore preferred that cobalt/nitrogen carbon nanomaterial dosage is 150~200mg/L.
Preferably, peroxydisulfate is selected from potassium persulfate or sodium persulfate.
It is furthermore preferred that using acetate buffer, phosphate buffer, 2- (Cyclohexylamino) ethanesulfonic acid buffer, dilute
Sulfuric acid and sodium hydroxide adjust the pH of waste water.
Preferably, after reaction, cobalt/nitrogen carbon nanomaterial is recycled, specific steps are as follows: obtained after suction filtration cobalt/
Nitrogen carbon nanomaterial is washed three times, and 60 DEG C of dry 12h in baking oven obtain cobalt/nitrogen carbon nanomaterial of regeneration, by 5 times
Still catalytic activity with higher after recycling.
ZIF-67 is by Co2+It is formed with 2-methylimidazole, the cobalt insertion porous carbon polyhedron tool formed after the high-temperature anneal
There are Co-N structure abundant and unique dodecahedron form, is the ideal catalyst for activating PS.
Cobalt of the invention/nitrogen carbon nanomaterial (Co/NC) catalyst removes excessive metal ion by pickling, and reduction is urged
The agent dissolution of metal ion and problem of environmental pollution during the reaction, also have that catalytic effect is stable, reusing is good
The advantages that.Cobalt/nitrogen carbon nanomaterial activation persulfate technology is that hardly degraded organic substance provides one newly in removal water body
Approach.
Compared with prior art, the invention has the following advantages:
1. the presoma ZIF-67 of Co/NC nano material of the present invention, for nitrogenous organic ligand, is introduced with 2-methylimidazole
Nitrogen-containing functional group, compared to conventional PS catalyst, which may be implemented better pollutant removal.
2. there is the contaminant removal process of Co/NC nano material activation PDS prepared by the present invention extensive pH to be applicable in model
It encloses, can carry out good removal to pollutant within the scope of 5~9 pH.
3. Co/NC nano material favorable dispersibility prepared by the present invention, seldom, secondary pollution is asked for dissolution during the reaction
It inscribes not serious.
4. Co/NC nano material regenerability prepared by the present invention is good, can have after filtering washing relatively stable
Catalytic performance.
5. catalyst of the present invention both can independent degradation of contaminant, can also by with other water pollution treatment process be combined drop
Solve pollutant.
Detailed description of the invention
Fig. 1 is the SEM scanning electron microscope (SEM) photograph of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone in embodiment 1；
Fig. 2 is unpickled cobalt/nitrogen carbon nanomaterial SEM scanning electron microscope (SEM) photograph in comparative example 1；
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of presoma ZIF-67 in comparative example 2；
Fig. 4 is the removal rate figure that embodiment 1 and comparative example 1-4 activate parachloroanilinum in peroxydisulfate PDS system；
Fig. 5 is cobalt/nitrogen carbon nanomaterial regeneration recycling repeatedly activation peroxoctisulphate parachloroanilinum removal rate
Figure；
Fig. 6 is the influence diagram that different inhibitor activate peroxydisulfate PDS system to cobalt/nitrogen carbon nanomaterial；
Fig. 7 is the removal rate figure that embodiment 13 and comparative example 8 activate peroxydisulfate PDS system mesoxalic acid；
Fig. 8 is the effect picture that cobalt/nitrogen carbon nanomaterial adsorbs parachloroanilinum；
Fig. 9 is the removal rate figure that embodiment 15 and comparative example 9 activate TOC in peroxydisulfate PDS system.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
In following embodiment, peroxydisulfate is sodium persulfate.
Embodiment 1
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.Black solid powder obtained is the derivative cobalt/nitrogen of organic backbone
Carbon nanomaterial, scanning electron microscope sem pattern is as shown in Figure 1, be in positive ten six sided structures, the ZIF-67 after annealing is bright
Aobvious surface atrophy is in fold shape.The cobalt simple substance of the complete not bulky grain of pickling exists, simultaneously because excessive cobalt is removed, in particle
There is more porous structure in surface.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, molten with phosphate-buffered
Liquid configures the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, the Co/NC after pickling is taken into 15mg
It is added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts timing, altogether
React 60min.Parachloroanilinum residual concentration is detected after specific reaction time point samples and is quenched with methanol, is calculated
Parachloroanilinum removal rate.Co is measured after reaction2+Dissolution is 0.42mg/L.
Comparative example 1
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h.Black solid powder obtained is that the derivative cobalt/nitrogen carbon of unpickled organic backbone is received
Rice material, scanning electron microscope sem pattern are as shown in Figure 2, it can be seen that positive 16 face mentions structure memory in particle not of uniform size
Cobalt simple substance, the obvious surface atrophy of ZIF-67 after annealing are in fold shape.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, slow with phosphate
Rush the simulated wastewater that solution allocation pH is 7.5.100mL simulated wastewater is added in 150mL beaker, unpickled Co/NC is taken
15mg is added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts to count
When, coreaction 60min.Parachloroanilinum residual concentration is examined after specific reaction time point samples and is quenched with methanol
It surveys, calculates parachloroanilinum removal rate.Co is measured after reaction2+Dissolution is 1.49mg/L.
Comparative example 2
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.Violet solid powder obtained is presoma
ZIF-67, scanning electron microscope sem pattern is as shown in figure 3, be in positive ten six sided structures, with the brown powder pattern phase after annealing
Seemingly, but smooth without the obvious surface ZIF-67 after annealing, particle is bigger than cobalt/nitrogen carbon after annealing.
(2) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, molten with phosphate-buffered
Liquid configures the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, takes 15mg in magnetic ZIF-67 presoma
Power is added with stirring in simulated wastewater, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts timing, coreaction
60min.Parachloroanilinum residual concentration is detected after specific reaction time point samples and is quenched with methanol, is calculated to chlorine
Aniline removal rate.Co is measured after reaction2+Dissolution is 2.42mg/L.
Comparative example 3
Select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, uses phosphate buffer solution
Configure the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, by the Co (NO of 0.207mg3)2·6H2O
It is added in simulated wastewater and keeps Co in simulated wastewater2+The Co that concentration and Co/NC are dissolved out after being added2+Concentration is consistent, is stirring evenly
2.5mM peroxydisulfate PDS is added afterwards, reaction starts timing, coreaction 60min.It samples and is used in combination in specific reaction time point
Methanol detects parachloroanilinum residual concentration after being quenched, and calculates parachloroanilinum removal rate.
Comparative example 4
Select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, uses phosphate buffer solution
Configure the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, 2.5mM peroxydisulfate PDS is added,
Reaction starts timing, coreaction 60min.Parachloroanilinum is remained after specific reaction time point samples and is quenched with methanol dense
Degree is detected, and parachloroanilinum removal rate is calculated.
The contaminant degradation curve of embodiment 1 and comparative example 1-4 as shown in figure 4, the Co/NC before and after pickling to parachloroanilinum
Degradation effect be better than PDS and individually degrade parachloroanilinum.Wherein unpickled Co/NC is slightly good to the degradation effect of parachloroanilinum
Co/NC after pickling can both realize 95% or more pollutant removal, but the Co/NC after pickling after reacting 60min
The Co dissolved out at the end of reaction2+Only 0.42mg/L, much smaller than the Co of unpickled Co/NC2+Dissolution.With Co/NC after pickling
The Co of dissolution2+The comparable Co of concentration2+Solution is only able to achieve the degradation of the parachloroanilinum less than 30%, ZIF-67 forerunner after 60min
Body is able to achieve about 70% parachloroanilinum degradation after 60min, and independent PDS is only able to achieve about 20% parachloroanilinum degradation.
Embodiment 2
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, molten with phosphate-buffered
Liquid configures the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, the Co/NC after pickling is taken into 15mg
It is added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 1mM peroxydisulfate PDS, reaction starts timing, anti-altogether
Answer 60min.Parachloroanilinum residual concentration is detected after specific reaction time point samples and is quenched with methanol, calculating pair
Chloroaniline removal rate.
Embodiment 3
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, molten with phosphate-buffered
Liquid configures the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, the Co/NC after pickling is taken into 15mg
It is added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 5mM peroxydisulfate PDS, reaction starts timing, anti-altogether
Answer 60min.Parachloroanilinum residual concentration is detected after specific reaction time point samples and is quenched with methanol, calculating pair
Chloroaniline removal rate.
The removal rate of different time points parachloroanilinum is as shown in table 1 below, as the oxidant PDS of addition increases, generation
Active material increases, and the removal rate of pollutant parachloroanilinum is also higher.
Table 1
Embodiment 4
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, molten with phosphate-buffered
Liquid configures the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, the Co/NC after pickling is taken into 2.5mg
It is added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts timing, altogether
React 60min.Parachloroanilinum residual concentration is detected after specific reaction time point samples and is quenched with methanol, is calculated
Parachloroanilinum removal rate.
Embodiment 5
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
The research of Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, molten with phosphate-buffered
Liquid configures the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, the Co/NC after pickling is taken into 7.5mg
It is added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts timing, altogether
React 60min.Parachloroanilinum residual concentration is detected after specific reaction time point samples and is quenched with methanol, is calculated
Parachloroanilinum removal rate.
Embodiment 6
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, molten with phosphate-buffered
Liquid configures the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, the Co/NC after pickling is taken into 20mg
It is added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts timing, altogether
React 60min.Parachloroanilinum residual concentration is detected after specific reaction time point samples and is quenched with methanol, is calculated
Parachloroanilinum removal rate.
The parachloroanilinum removal rate of embodiment 1, comparative example 4 and embodiment 4-6 is as shown in table 2 below, with the catalysis of addition
Agent increases, and the removal rate of pollutant parachloroanilinum also increases therewith.
Table 2
Embodiment 7
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt insertion nitrogen carbon nanomaterial of organic backbone: by ZIF-67 presoma with 2 under argon atmosphere
DEG C/min is warming up to 900 DEG C, maintains 3h, the black powder product of generation is put into 0.5M sulfuric acid solution pickling for 24 hours with removal
Excessive cobalt ions is dried overnight after filtering and being washed with water 3 times.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, slow with acetate
Fliud flushing configures the simulated wastewater that pH is 5.0.100mL simulated wastewater is added in 150mL beaker, the Co/NC after pickling is taken
15mg is added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts to count
When, coreaction 60min.Parachloroanilinum residual concentration is examined after specific reaction time point samples and is quenched with methanol
It surveys, calculates parachloroanilinum removal rate.
Embodiment 8
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
The research of Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt insertion nitrogen carbon nanomaterial of organic backbone: by ZIF-67 presoma with 2 under argon atmosphere
DEG C/min is warming up to 900 DEG C, maintains 3h, the black powder product of generation is put into 0.5M sulfuric acid solution pickling for 24 hours with removal
Excessive cobalt ions is dried overnight after filtering and being washed with water 3 times.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, with 2- (hexamethylene ammonia
Base) ethanesulfonic acid buffer configuration pH be 9.0 simulated wastewater.100mL simulated wastewater is added in 150mL beaker, after pickling
Co/NC take 15mg to be added in simulated wastewater under magnetic stirring, be stirring evenly and then adding into 2.5mM peroxydisulfate PDS, instead
It should start timing, coreaction 60min.To parachloroanilinum residual concentration after specific reaction time point samples and is quenched with methanol
It is detected, calculates parachloroanilinum removal rate.
The parachloroanilinum removal rate of embodiment 1,7 and 8 is as shown in table 3 below, and the Co/NC after pickling is within the scope of 5~9 pH
It shows to show that the catalyst can activate PDS within the scope of wider pH to the good degradation effect of parachloroanilinum.
Table 3
Embodiment 9
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, in order to avoid having
The influence of machine buffer solution, the simulated wastewater for being 5.0 with dilute sulfuric acid configuration pH.It is useless that 100mL simulation is added in 150mL beaker
Water, takes 15mg to be added in simulated wastewater under magnetic stirring the Co/NC after pickling, crosses two being stirring evenly and then adding into 2.5mM
Sulfate PDS, reaction start timing, coreaction 2min.To chlorine after specific reaction time point samples and is quenched with methanol
Aniline residue concentration is detected, and parachloroanilinum removal rate is calculated.
Embodiment 10
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
The research of Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, in order to avoid having
The influence of machine buffer solution, the simulated wastewater for being 7.5 with sodium hydroxide configuration pH.It is useless that 100mL simulation is added in 150mL beaker
Water, takes 15mg to be added in simulated wastewater under magnetic stirring the Co/NC after pickling, crosses two being stirring evenly and then adding into 2.5mM
Sulfate PDS, reaction start timing, coreaction 2min.To chlorine after specific reaction time point samples and is quenched with methanol
Aniline residue concentration is detected, and parachloroanilinum removal rate is calculated.
Embodiment 11
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used to activate peroxydisulfate removal
Recalcitrant chemicals, the specific steps are as follows:
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, in order to avoid organic slow
The influence for rushing solution, the simulated wastewater for being 9.0 with sodium hydroxide configuration pH.100mL simulated wastewater is added in 150mL beaker,
It takes 15mg to be added in simulated wastewater under magnetic stirring the Co/NC after pickling, is being stirring evenly and then adding into 2.5mM peroxy-disulfuric acid
Salt PDS, reaction start timing, coreaction 2min.To parachloroanilinum after specific reaction time point samples and is quenched with methanol
Residual concentration is detected, and parachloroanilinum removal rate is calculated.
The parachloroanilinum removal rate of embodiment 9-11 is as shown in table 4 below, and the Co/NC after pickling is equal within the scope of 5~9 pH
It shows to show that the catalyst can activate PDS within the scope of wider pH to the good degradation effect of parachloroanilinum.
Table 4
Comparative example 5
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, and 5000mM methanol is added
(MeOH), the simulated wastewater for being 5.0 with acetate buffer configuration pH.100mL simulated wastewater is added in 150mL beaker, it will
Co/NC after pickling takes 15mg to be added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 2.5mM peroxydisulfate
PDS, reaction start timing, coreaction 60min.It is residual to parachloroanilinum after specific reaction time point samples and is quenched with methanol
It stays concentration to be detected, calculates parachloroanilinum removal rate.
Comparative example 6
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, is separately added into 5000mM
The tert-butyl alcohol (TBA), the simulated wastewater for being 5.0 with acetate buffer configuration pH.It is useless that 100mL simulation is added in 150mL beaker
Water, takes 15mg to be added in simulated wastewater under magnetic stirring the Co/NC after pickling, crosses two being stirring evenly and then adding into 2.5mM
Sulfate PDS, reaction start timing, coreaction 60min.To chlorine after specific reaction time point samples and is quenched with methanol
Aniline residue concentration is detected, and parachloroanilinum removal rate is calculated.
Comparative example 7
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) target contaminant that parachloroanilinum is degradation is selected, parachloroanilinum concentration is 0.15mM, is separately added into 1000mM benzene
Phenol, the simulated wastewater for being 5.0 with acetate buffer configuration pH.100mL simulated wastewater is added in 150mL beaker, by pickling
Co/NC afterwards takes 15mg to be added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS,
Reaction starts timing, coreaction 60min.Parachloroanilinum is remained after specific reaction time point samples and is quenched with methanol dense
Degree is detected, and parachloroanilinum removal rate is calculated.
The removal rate of embodiment 7 and comparative example 5-7 are as shown in Figure 6.The present embodiment is for investigating various inhibitor to pickling
The inhibitory effect of Co/NC activation PDS afterwards.MeOH can inhibit hydroxyl radical free radical and potentiometric titrations, and TBA can
Hydroxyl radical free radical is inhibited.MeOH and TBA unobvious to the inhibitory effect of parachloroanilinum is because both inhibitor have
There is stronger hydrophily, it can not be anti-in the hydroxyl radical free radical and potentiometric titrations and hydrophobic contaminant that hydrophobic surface generates
It should be inhibited before.The inhibitory effect ratio TBA of MeOH worse is because the hydrophily of MeOH is stronger.Phenol is one kind to catalysis
Hydroxyl radical free radical and potentiometric titrations that agent surface generates have the inhibitor of inhibitory effect, the experimental results showed that phenol is to right
The degradation of chloroaniline has good inhibitory effect.Therefore mainly passing through parachloroanilinum is adsorbed on catalyst for the degradation of parachloroanilinum
What the radical reaction generated behind surface with catalyst surface carried out.
Embodiment 12
Select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, is matched with acetate buffer
Set the simulated wastewater that pH is 5.0.100mL simulated wastewater is added in 150mL beaker, takes 15mg in magnetic the Co/NC after pickling
Power is added with stirring in simulated wastewater, is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts timing, coreaction
12min.Parachloroanilinum residual concentration is detected after specific reaction time point samples and is quenched with methanol, is calculated to chlorine
Aniline removal rate.Suction filtration recycling is carried out to catalyst after the completion of reaction, washes three times and drying obtains regenerated catalyst, altogether
Recycling 5 times.Experimental result is as shown in figure 5, the Co/NC after pickling remains to reach 100% when reusing for second
Parachloroanilinum removal is still able to achieve 93.9% parachloroanilinum removal after recycling five times.This is the result shows that after pickling
Co/NC has remarkable result for activating PDS degradation parachloroanilinum simulated wastewater, and remains to after carrying out 5 recyclings
Keep stability.
Embodiment 13
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select oxalic acid for the target contaminant of degradation, concentration of oxalic acid 0.15mM.100mL is added in 150mL beaker
Co/NC after pickling is taken 15mg to be added in simulated wastewater under magnetic stirring, is being stirring evenly and then adding by simulated wastewater
2.5mM peroxydisulfate PDS, reaction start timing, coreaction 60min.
Comparative example 8
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select oxalic acid for the target contaminant of degradation, concentration of oxalic acid 0.15mM is added 5000mM methanol (MeOH).
100mL simulated wastewater is added in 150mL beaker, takes 15mg that simulated wastewater is added under magnetic stirring the Co/NC after pickling
In, it is being stirring evenly and then adding into 2.5mM peroxydisulfate PDS, reaction starts timing, coreaction 60min.
The oxalic acid removal rate of embodiment 13 and comparative example 8 samples in specific reaction time point as shown in Figure 7 and uses methanol
Oxalic acid residual concentration is detected after being quenched, calculating oxalate removal rate.Oxalic acid is a kind of dirt more more hydrophilic than parachloroanilinum
Object is contaminated, the removal rate that oxalic acid after the MeOH of 5M is added is only lower by 0.9% than being added without the removal rate of oxalic acid, this shows hydroxyl radical free radical
It is not the unique channel of parachloroanilinum degradation with potentiometric titrations, there are non-free radical approach to degrade to pollutant.
Embodiment 14
A kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone and its be used for Recalcitrant chemicals to chlorine
Aniline absorption, specific step is as follows
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM, with phosphate salt buffer
Liquid configures the simulated wastewater that pH is 7.5.100mL simulated wastewater is added in 150mL beaker, the Co/NC after pickling is taken into 15mg
It is added in simulated wastewater under magnetic stirring, reaction starts timing, coreaction 60min.It is sampled simultaneously in specific reaction time point
Parachloroanilinum residual concentration is detected after being quenched with methanol, calculates parachloroanilinum removal rate.Experimental results are shown in figure 8,
Co/NC after pickling is able to achieve 36.3% removal to parachloroanilinum in 60min.
Embodiment 15
(1) preparation of presoma ZIF-67: the Co (NO of stirring and dissolving 2.50g in 250mL methanol3)2·6H2Co is made in O
(NO3)2Solution for standby；2-methylimidazole solution for standby is made in the 2-methylimidazole of stirring and dissolving 3.28g in 250mL methanol；In
Under stirring, to Co (NO3)2It is poured slowly into 2-methylimidazole solution in solution, stands aging for 24 hours at room temperature, is centrifugated formation
Purple product is simultaneously washed 3 times with methanol, dries 12h at 60 DEG C in baking oven.
(2) preparation of the derivative cobalt/nitrogen carbon nanomaterial of organic backbone: under argon atmosphere by ZIF-67 presoma with 2 DEG C/
Min's is warming up to 900 DEG C, maintains 3h, it is excessive to remove for 24 hours that the black powder product of generation is put into pickling in 0.5M sulfuric acid solution
Cobalt ions, after filtering and being washed with water 3 times dry overnight.
(3) select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM.In 150mL beaker
100mL simulated wastewater is added, takes 15mg to be added in simulated wastewater under magnetic stirring the Co/NC after pickling, is stirring evenly
2.5mM peroxydisulfate PDS is added afterwards, reaction starts timing, coreaction 20h.It samples and calculates in specific reaction time point
TOC (total organic carbon) removal rate.
Comparative example 9
Select parachloroanilinum for the target contaminant of degradation, parachloroanilinum concentration is 0.15mM.It is added in 150mL beaker
2.5mM peroxydisulfate PDS is added in 100mL simulated wastewater, stirring, and reaction starts timing, coreaction 20h.Specifically reacting
Point in time sampling simultaneously calculates TOC removal rate.
The TOC of embodiment 15 and comparative example 9 goes division result as shown in figure 9, showing that the addition of persulfate removes TOC
To facilitation.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of cobalt derived from organic metal framework/nitrogen carbon nanomaterial preparation method, which is characterized in that specific steps are such as
Under:
(1) preparation of Co/NC nano material presoma organometallic skeletal ZIF-67: stirring and dissolving Co (NO in methyl alcohol3)2·
6H2Co (NO is made in O3)2Solution；2-methylimidazole solution is made in stirring and dissolving 2-methylimidazole in methyl alcohol；To Co (NO3)2It is molten
2-methylimidazole solution is poured into liquid, is stood aging, centrifugation, washing, drying at room temperature, is obtained ZIF-67；
(2) cobalt derived from metal organic framework ZIF-67/nitrogen carbon nanomaterial preparation: step (1) is obtained into ZIF-67 and is carried out
Annealing obtains cobalt/nitrogen carbon nanomaterial after pickling, washing, drying.
2. cobalt derived from a kind of organic metal framework according to claim 1/nitrogen carbon nanomaterial preparation method, special
Sign is, Co (NO in step (1)3)2Co (NO is added in every 250mL methanol for solution3)2·6H2The quality of O is 2.50g.
3. cobalt derived from a kind of organic metal framework according to claim 1/nitrogen carbon nanomaterial preparation method, special
Sign is, 2-methylimidazole solution in step (1), and 2-methylimidazole quality used in every 250mL methanol is 3.28g.
4. cobalt derived from a kind of organic metal framework according to claim 1/nitrogen carbon nanomaterial preparation method, special
Sign is, in step (1): ageing time is that for 24 hours, drying temperature is 60 DEG C, drying time 12h.
5. cobalt derived from a kind of organic metal framework according to claim 1/nitrogen carbon nanomaterial preparation method, special
Sign is, in step (2) the step of annealing are as follows: under argon atmosphere, is warming up to 900 DEG C with 2 DEG C/min, maintains 3h.
6. cobalt derived from a kind of organic metal framework according to claim 1/nitrogen carbon nanomaterial preparation method, special
Sign is, in step (2) the step of pickling are as follows: carries out pickling using the sulfuric acid solution of 0.5M, pickling time is for 24 hours.
7. a kind of derivative cobalt/nitrogen carbon nanomaterial of metal organic frame, which is characterized in that appoint using described in claim 1-6
What a kind of preparation method of the derivative cobalt/nitrogen carbon nanomaterial of the metal organic frame of anticipating was prepared.
8. the application of cobalt derived from a kind of organic metal framework according to claim 7/nitrogen carbon nanomaterial, feature exist
In for activating peroxydisulfate removal Pollutants in Wastewater, specific steps are as follows:
Cobalt/nitrogen carbon nanomaterial is added in waste water after mixing evenly, peroxydisulfate is added and is allowed to come into full contact with, stirring is anti-
It answers, hardly degraded organic substance in water of degrading.
9. the application of cobalt derived from a kind of organic metal framework according to claim 8/nitrogen carbon nanomaterial, feature exist
In the dosage of peroxydisulfate is 1~5mM, and cobalt/nitrogen carbon nanomaterial dosage is 25~200mg/L, and the pH of waste water is
5~9.
10. the application of cobalt derived from a kind of organic metal framework according to claim 8/nitrogen carbon nanomaterial, feature
It is, after reaction, cobalt/nitrogen carbon nanomaterial is recycled, specific steps are as follows: obtains cobalt/nitrogen carbon nanometer material after suction filtration
Material is washed three times, and 60 DEG C of dry 12h in baking oven obtain cobalt/nitrogen carbon nanomaterial of regeneration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910698044.9A CN110479224A (en) | 2019-07-31 | 2019-07-31 | Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910698044.9A CN110479224A (en) | 2019-07-31 | 2019-07-31 | Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110479224A true CN110479224A (en) | 2019-11-22 |
Family
ID=68549068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910698044.9A Pending CN110479224A (en) | 2019-07-31 | 2019-07-31 | Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110479224A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| CN110961159A (en) * | 2019-12-31 | 2020-04-07 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
| CN111001427A (en) * | 2019-12-24 | 2020-04-14 | 山西大学 | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof |
| CN111205477A (en) * | 2020-02-28 | 2020-05-29 | 三峡大学 | Preparation of ZIF-67 catalyst and application of catalyst in degradation of antibiotics such as tetracycline |
| CN111302476A (en) * | 2020-02-27 | 2020-06-19 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN111547701A (en) * | 2020-05-12 | 2020-08-18 | 湖南垚恒环境科技有限公司 | Magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material and preparation method thereof |
| CN111569929A (en) * | 2020-05-18 | 2020-08-25 | 石河子大学 | Co-MOF derived cobalt/nitrogen/carbon composite material and preparation method thereof |
| CN111672474A (en) * | 2020-06-28 | 2020-09-18 | 福州大学 | Magnetic nitrogen-doped carbon oxide nanotube material and preparation method and application thereof |
| CN111760555A (en) * | 2020-06-08 | 2020-10-13 | 天津科技大学 | Preparation method and application of ZIF-based low-temperature adsorption material |
| CN112169822A (en) * | 2020-10-21 | 2021-01-05 | 南京大学 | Nitrogen-doped hollow carbon polyhedron @ carbon nanotube-based single-atom cobalt catalyst for efficiently activating persulfate and preparation method thereof |
| CN112264082A (en) * | 2020-11-24 | 2021-01-26 | 中国环境科学研究院 | MOFs-based cobalt/nitrogen doped carbon material capable of activating peroxymonosulfate and preparation method and application thereof |
| CN112892593A (en) * | 2021-01-18 | 2021-06-04 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
| CN112958140A (en) * | 2021-03-05 | 2021-06-15 | 天津大学 | Co-PCN catalyst capable of regulating and controlling active site as well as preparation method and application thereof |
| CN113231029A (en) * | 2021-05-28 | 2021-08-10 | 南通大学 | Preparation method of activated carbon fiber functional material with efficient decolorizing performance |
| CN114436376A (en) * | 2022-01-31 | 2022-05-06 | 浙江佰辰低碳科技有限公司 | Electrode material for in-situ growth of Prussian blue analogue by taking MOF (Metal organic framework) derived carbon nanotube array as substrate and preparation method of electrode material |
| CN114522713A (en) * | 2022-02-23 | 2022-05-24 | 中国石油大学(华东) | Preparation method and application of cobalt nanoparticle/boron nitride composite material |
| CN114713259A (en) * | 2022-04-02 | 2022-07-08 | 中山大学 | Preparation of cobalt-carbon-nitrogen hollow polyhedral catalyst and application of cobalt-carbon-nitrogen hollow polyhedral catalyst in degradation of emerging pollutants |
| CN115025796A (en) * | 2022-04-29 | 2022-09-09 | 南通大学 | Biomass-loaded MOFs-derived composite catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
| CN107381659A (en) * | 2017-06-28 | 2017-11-24 | 江苏大学 | The method that template prepares aspherical hollow structure nanocages composite |
| CN109331874A (en) * | 2018-09-19 | 2019-02-15 | 上海电力学院 | A kind of preparation method of three-dimensional porous carbon coating Co-MOF catalyst material |
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| KR101986247B1 (en) * | 2017-12-14 | 2019-06-07 | 한국과학기술연구원 | Process for preparation of Negative electrode active material comprising N-doped carbon-layer coated porous metal oxide and secondary battery using the same |
-
2019
- 2019-07-31 CN CN201910698044.9A patent/CN110479224A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
| CN107381659A (en) * | 2017-06-28 | 2017-11-24 | 江苏大学 | The method that template prepares aspherical hollow structure nanocages composite |
| KR101986247B1 (en) * | 2017-12-14 | 2019-06-07 | 한국과학기술연구원 | Process for preparation of Negative electrode active material comprising N-doped carbon-layer coated porous metal oxide and secondary battery using the same |
| CN109331874A (en) * | 2018-09-19 | 2019-02-15 | 上海电力学院 | A kind of preparation method of three-dimensional porous carbon coating Co-MOF catalyst material |
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
Non-Patent Citations (1)
| Title |
|---|
| YING LIU ET AL.: "Activation of persulfate with metal-organic framework-derived nitrogen-doped porous Co@C nanoboxes for highly efficient p-Chloroaniline removal", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| CN111001427A (en) * | 2019-12-24 | 2020-04-14 | 山西大学 | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof |
| CN110961159B (en) * | 2019-12-31 | 2022-11-15 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
| CN110961159A (en) * | 2019-12-31 | 2020-04-07 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
| CN111302476A (en) * | 2020-02-27 | 2020-06-19 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN111205477A (en) * | 2020-02-28 | 2020-05-29 | 三峡大学 | Preparation of ZIF-67 catalyst and application of catalyst in degradation of antibiotics such as tetracycline |
| CN111205477B (en) * | 2020-02-28 | 2022-04-22 | 三峡大学 | Preparation of ZIF-67 catalyst and application of catalyst in degradation of antibiotics such as tetracycline |
| CN111547701A (en) * | 2020-05-12 | 2020-08-18 | 湖南垚恒环境科技有限公司 | Magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material and preparation method thereof |
| CN111569929A (en) * | 2020-05-18 | 2020-08-25 | 石河子大学 | Co-MOF derived cobalt/nitrogen/carbon composite material and preparation method thereof |
| CN111760555A (en) * | 2020-06-08 | 2020-10-13 | 天津科技大学 | Preparation method and application of ZIF-based low-temperature adsorption material |
| CN111760555B (en) * | 2020-06-08 | 2023-03-14 | 天津科技大学 | Preparation method and application of ZIF-based low-temperature adsorption material |
| CN111672474A (en) * | 2020-06-28 | 2020-09-18 | 福州大学 | Magnetic nitrogen-doped carbon oxide nanotube material and preparation method and application thereof |
| CN112169822A (en) * | 2020-10-21 | 2021-01-05 | 南京大学 | Nitrogen-doped hollow carbon polyhedron @ carbon nanotube-based single-atom cobalt catalyst for efficiently activating persulfate and preparation method thereof |
| CN112169822B (en) * | 2020-10-21 | 2021-11-16 | 南京大学 | Nitrogen-doped hollow carbon polyhedron @ carbon nanotube-based single-atom cobalt catalyst for efficiently activating persulfate and preparation method thereof |
| CN112264082A (en) * | 2020-11-24 | 2021-01-26 | 中国环境科学研究院 | MOFs-based cobalt/nitrogen doped carbon material capable of activating peroxymonosulfate and preparation method and application thereof |
| CN112892593A (en) * | 2021-01-18 | 2021-06-04 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
| CN112958140A (en) * | 2021-03-05 | 2021-06-15 | 天津大学 | Co-PCN catalyst capable of regulating and controlling active site as well as preparation method and application thereof |
| CN113231029A (en) * | 2021-05-28 | 2021-08-10 | 南通大学 | Preparation method of activated carbon fiber functional material with efficient decolorizing performance |
| CN114436376A (en) * | 2022-01-31 | 2022-05-06 | 浙江佰辰低碳科技有限公司 | Electrode material for in-situ growth of Prussian blue analogue by taking MOF (Metal organic framework) derived carbon nanotube array as substrate and preparation method of electrode material |
| CN114522713A (en) * | 2022-02-23 | 2022-05-24 | 中国石油大学(华东) | Preparation method and application of cobalt nanoparticle/boron nitride composite material |
| CN114522713B (en) * | 2022-02-23 | 2023-04-14 | 中国石油大学(华东) | Preparation method and application of cobalt nanoparticle/boron nitride composite material |
| CN114713259A (en) * | 2022-04-02 | 2022-07-08 | 中山大学 | Preparation of cobalt-carbon-nitrogen hollow polyhedral catalyst and application of cobalt-carbon-nitrogen hollow polyhedral catalyst in degradation of emerging pollutants |
| CN114713259B (en) * | 2022-04-02 | 2024-02-23 | 中山大学 | Preparation of cobalt carbon nitrogen hollow polyhedral catalyst and application thereof in degradation of emerging pollutants |
| CN115025796A (en) * | 2022-04-29 | 2022-09-09 | 南通大学 | Biomass-loaded MOFs-derived composite catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110479224A (en) | Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application | |
| CN111790422B (en) | Graphitized nitrogen-complexed Fe (III) -Fe0Catalyst, and synthesis method and application thereof | |
| CN106807376B (en) | Magnetic nano composite catalyst and preparation method and application thereof | |
| CN110776049B (en) | Method for treating organic wastewater by activating peroxymonosulfate with functionalized zirconium-based metal organic framework/protonated carbon nitride composite material | |
| CN110550686B (en) | Treatment method of heterocyclic organic matter-containing wastewater and obtained adsorption material | |
| CN110743549B (en) | Preparation method of copper-based heterogeneous catalyst taking activated carbon spheres as carrier for wet oxidation | |
| CN111889125B (en) | Defect-rich monatomic material and preparation method and application thereof | |
| CN110152702A (en) | Derivative nitrogen carbon nanomaterial of a kind of organic backbone and its preparation method and application | |
| CN102151543A (en) | Preparation method, product and application of catalytic activity nano particle loaded absorbent | |
| CN107737594B (en) | Catalyst for degrading formaldehyde wastewater and preparation method and application thereof | |
| CN113209968B (en) | Preparation method and application of magnetic copper-iron bimetallic biomass charcoal microsphere | |
| CN110330091A (en) | Magnetic green material function Carbon fibe and its preparation method and application based on the catalysis of light Fenton | |
| CN109289851A (en) | One-step synthesis prepares Fe3O4The method of/mesoporous carbon composite material and its catalyzing oxidizing degrading sulfamethazine | |
| CN109908899A (en) | A kind of TiO2Load the preparation method and applications of monatomic Co catalyst | |
| CN112844350A (en) | Titanium-containing blast furnace slag loaded nano zero-valent iron material and preparation method and application thereof | |
| CN104841451A (en) | Preparation of Cu doped MnO2 mesoporous material and application of material in Fenton-like water treatment advanced oxidation technology | |
| CN111533237A (en) | Method for treating antibiotic wastewater by using manganese ion doped metal organic framework material | |
| CN105056986B (en) | A kind of method and catalyst applications for preparing lamellar hydroxyl bismuth subnitrate photocatalyst | |
| CN110449162B (en) | Modified manganese slag-iron vitriol slag mixed slag catalyst and preparation method and application thereof | |
| CN106238024A (en) | A kind of renovation process adsorbing zinc sulfate electrodeposition waste liquid impurity activity charcoal | |
| CN114042448B (en) | Preparation method and application of Mn-MOF-based two-dimensional sheet manganese oxide/mesoporous carbon catalyst | |
| CN108144583A (en) | It is a kind of novel except the preparation method of formaldehyde activity charcoal | |
| WO2021258856A1 (en) | Photocatalyst and application thereof in photocatalytic environmentally-friendly treatment of power batteries | |
| CN115382551B (en) | Three-dimensional carbonaceous functional cathode material based on potassium ferrate modification, and preparation method and application thereof | |
| CN108439529B (en) | Method for removing rhodamine B in water body by utilizing bismuth ferrite/bismuth tungstate heterojunction photocatalytic material |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191122 |