CN116747869A - Waste adsorbent-based CO treatment method 2 Reduced monoatomic catalyst and method for preparing same - Google Patents
Waste adsorbent-based CO treatment method 2 Reduced monoatomic catalyst and method for preparing same Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 239000003463 adsorbent Substances 0.000 title claims abstract description 74
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000011278 co-treatment Methods 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 238000009713 electroplating Methods 0.000 claims abstract description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000005416 organic matter Substances 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004202 carbamide Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims 1
- 239000002910 solid waste Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000004973 liquid crystal related substance Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- -1 nitrogenous organic compound Chemical class 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
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- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 238000010792 warming Methods 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- HPJKLCJJNFVOEM-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrochloride Chemical compound Cl.NC1=NC(N)=NC(N)=N1 HPJKLCJJNFVOEM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a waste adsorbent-based catalyst for CO 2 The reduced monoatomic catalyst and the preparation method thereof comprise monoatomic heavy metals, wherein the surfaces of the monoatomic heavy metals are covered with carbon nanotubes, and the carbon nanotubes have porous structures. The preparation method of the monoatomic catalyst comprises the following steps: s1, adding a carbon-based adsorbent into an adsorption filter tank, and filtering electroplating wastewater containing heavy metals; s2, willThe carbon-based adsorbent is adsorbed and regenerated, and the process is repeated for a plurality of times until the concentration of heavy metals in the wastewater is not changed any more, so that a waste adsorbent is obtained; s3, uniformly mixing the waste adsorbent and the nitrogenous organic matters, and then performing programmed heating carbonization to obtain the waste adsorbent-based CO used for the treatment of the waste adsorbent 2 Reduced monoatomic catalysts. The catalyst has the characteristics of low cost, good conductivity and excellent CO selectivity, greatly reduces the harm of solid waste and heavy metals to the environment, and has wide market prospect.
Description
Technical Field
The invention belongs to the field of solid waste recycling, and in particular relates to a waste adsorbent-based solid waste recycling method for CO 2 Reduced monoatomic catalysts and methods of making the same.
Background
The advent of the industrial revolution has meant that the efficiency of human use of energy has risen again to a new step. However, while fossil fuel is consumed excessively to obtain heat energy, electric energy and fossil energy therein, a large amount of C element is used for stabilizing CO 2 The form of the gas is vented to the atmosphere. Such a gas capable of absorbing infrared radiant heat is one of the main pushers for global warming. The recent data from the National Ocean and Atmosphere Administration (NOAA) show that CO in the global atmosphere 2 The concentration is novel and high, and 419ppm is broken through. According to Paris's agreement and international energy agency's estimation and requirements, the global warming cannot be controlled within 1.5 ℃ in the middle of this century, which will have disastrous consequences in the future. Active carbon capture and conversion has therefore become a focus of attention and research focus.
Electrocatalytic reduction of CO 2 (ECO 2 RR) can be used to treat excessive CO 2 The conversion to a more stable form reduces the impact on the atmosphere. The converted products such as methane, CO, methanol, etc. are important chemical raw materials, thus ECO 2 RR is a potential carbon negative technology. Furthermore, maximum conversion efficiency can be achieved with very Small Amounts of Catalyst (SACs) at the monoatomic level, thus ECO 2 RR has sufficient market prospect.
At present, SACs are prepared mainly by anchoring heavy metal atoms or noble metals such as Ag and Au with carbon substrate materials such as graphene, metal Organic Frameworks (MOFs), covalent Organic Frameworks (COFs), carbon Nanotubes (CNTs) and the like, and catalyzing the heavy metal atoms or the noble metalsThe agent has excellent conductivity and can efficiently convert CO 2 Is converted into high-purity CO, formic acid, methanol, ethanol and other fuel or chemical production raw materials.
However, the following problems remain in the current preparation of SACs:
(1) The price of the synthetic SACs carbon matrix is too high:
the use of graphene, COFs, MOFs, CNTs and other substances as carbon substrates can greatly increase the catalyst cost. The preparation of these carbon substrates is quite complex, and the unit cost is too high, and the price can be from tens of units per gram to hundreds of units per gram. In addition, the synthesis method of part of carbon matrix materials is complicated, and the yield is low. Taking ZIF-8 commonly used in MOFs as an example, zinc nitrate and dimethyl imidazole are mixed in methanol solution to prepare a framework, precious metal is adsorbed, and after high-temperature carbonization, the precious metal can replace central atom zinc to generate SACs. The yield of SACs thus prepared is generally less than 5%, mainly due to the extremely low yield of ZIF-8, which wastes a large amount of dimethylimidazole and zinc nitrate.
(2) The price of noble metals is also very high
In the traditional preparation of SACs, precious metals such as Ag, au and Pt are used as catalysts, and the addition amount of the precious metals is relatively small when the SACs are synthesized, but the price of hundreds of yuan per gram (the price of Au and Pt is about 400 yuan per gram) still further increases the manufacturing cost of the catalysts.
In summary, how to find the replacement products of the expensive carbon substrate material and the noble metal, thereby greatly reducing the material investment and the cost, and solving the defects existing in the prior art is a problem to be solved.
Disclosure of Invention
In order to overcome the defects, the invention takes the waste heavy metal adsorbent as the raw material, only adds nitrogen-containing organic matters, and realizes high performance for CO by regulating and controlling the temperature programming 2 Preparation of reduced monoatomic catalysts. The catalyst has the characteristics of good conductivity and excellent CO selectivity. On the other hand, the invention prepares the catalyst by taking the water treatment waste as the raw material, thereby fully realizing the high-value recovery of the solid waste and the stabilization of the heavy metalsThe harm of solid waste and heavy metal to the environment is reduced. And the preparation of the traditional SACs carbon substrate material and noble metal is not involved, so that the cost of the catalyst can be greatly reduced, and the original cost of the catalyst of hundreds of yuan per gram is reduced in an order of magnitude. Therefore, the invention has wide market prospect.
It is an object of the present invention to provide a waste adsorbent based catalyst for CO 2 The reduced single-atom catalyst comprises single-atom heavy metals, wherein the surfaces of the single-atom heavy metals are covered with carbon nanotubes, and the carbon nanotubes have porous structures.
Further, the heavy metal is selected from one or more of nickel, cadmium, copper, iron, cobalt, manganese, chromium, zinc, lead and antimony.
Further, the heavy metal is nickel.
Further, the diameter of the carbon nanotube is 150-250nm.
It is another object of the present invention to provide the above waste adsorbent-based catalyst for CO 2 A method for preparing a reduced monoatomic catalyst comprising the steps of:
s1, adding a carbon-based adsorbent into an adsorption filter tank, and filtering electroplating wastewater containing heavy metals;
s2, adsorbing and regenerating the carbon-based adsorbent, and repeating for a plurality of times until the concentration of heavy metals in the wastewater is not changed any more to obtain a waste adsorbent;
s3, uniformly mixing the waste adsorbent and the nitrogenous organic matters, and then performing programmed heating carbonization to obtain the waste adsorbent-based CO used for the treatment of the waste adsorbent 2 Reduced monoatomic catalysts.
Further, the content of nickel element in the electroplating wastewater containing heavy metals is 150-250mg/L.
Further, the carbon-based adsorbent is selected from one or more of activated carbon, biochar and macroporous resin.
Further, the nitrogen-containing organic matter is selected from one or more of dicyandiamide, melamine chloride, urea and thiourea.
Further, in the step S3, the mass ratio of the waste adsorbent to the nitrogen-containing organic matter is 1 (5-10).
Further, in step S3, the programmed temperature is carbonized to: heating to 500-600deg.C at 2-5deg.C/min, and maintaining for 5-8 hr; heating to 900-1100 deg.C at 3-6deg.C/min, and maintaining for 2 hr.
In the invention, the priority of single heavy metal in heavy metal wastewater is required to be certain, namely the concentration of main heavy metal has a remarkable difference from the concentration of other heavy metals, the nickel-containing electroplating wastewater of an electroplating plant is taken as a main heavy metal source, wherein the Ni content is 182.94mg/L, and the concentrations of the other heavy metals (mainly Cd, cu, fe, co, mn) are all less than 5mg/L.
It is worth mentioning that in the invention, the size of heavy metal in the catalyst can be regulated and controlled by a specific temperature programming means, the heavy metal element with single atomic state can be prepared, and the carbon nano tube with porous structure can be generated on the surface of the heavy metal, thereby greatly improving the catalytic efficiency of the catalyst. The temperature program includes three phases: the first stage is at room temperature to 550 ℃, the second stage is at 550 ℃ for a maintaining time, and the third stage is at 550 ℃ and is at 1000 ℃. The primary function of the first stage is to make C 3 N 4 Stable formation, the second stage serving to further stabilize C 3 N 4 The third stage is for C 3 N 4 Is disintegrated.
Further, the programmed temperature rise control for generating the efficient and stable monoatomic catalyst is as follows:
the first step: raising the temperature from room temperature to 550 ℃ at a heating rate of 2.5 ℃/min;
and a second step of: maintaining the temperature at 550 ℃ for 6 hours;
and a third step of: the temperature was raised from 550℃to 1000℃at a heating rate of 5℃per minute and maintained at 1000℃for 2 hours, followed by natural cooling.
The beneficial effects of the invention are as follows:
1. waste adsorbent-based CO according to the invention 2 The reduced monoatomic catalyst has the advantages of cheap and easily available raw materials, wide sources, simple preparation method and only needsThe temperature rising speed is regulated and controlled, so that the preparation can be performed on a large scale, and the yield is high.
2. The catalyst raw material is common waste of the water treatment process, belongs to hazardous waste, has great harm to the environment, can realize high-value recovery of solid waste by fully utilizing the waste, and reduces the pollution to the environment.
3. By the specific preparation method, the single-atom catalyst can be obtained, and the catalyst can efficiently convert CO 2 The catalyst is CO, has excellent performance and good market prospect.
Drawings
Fig. 1 shows a surface scanning electron microscope picture of the waste adsorbent in step S2 of example 1.
Figure 2 shows the appearance of the monoatomic catalyst prepared in example 1.
FIG. 3 shows scanning electron micrographs of the nitrogen atom catalysts prepared in example 1 and comparative example 2;
wherein, the liquid crystal display device comprises a liquid crystal display device,
FIG. 3a is a scanning electron microscope image of the monoatomic catalyst prepared in example 1;
FIG. 3b is a single-atom-catalyst spherical aberration electron microscope image of example 1;
fig. 3c is a scanning electron microscope picture of the nanoparticle catalyst prepared in comparative example 2.
FIG. 4 shows the adsorption capacity of the monoatomic catalyst prepared in example 1;
wherein, the liquid crystal display device comprises a liquid crystal display device,
FIG. 4a is a BET and pore distribution of a monoatomic catalyst;
FIG. 4b CO for a monoatomic catalyst 2 Adsorption capacity.
Figure 5 shows the selectivity of the single-atom catalysts prepared with different spent adsorbents for examples 1-3 and the nanoparticle catalysts prepared for comparative example 2 to electrocatalytic products.
FIG. 6 shows the electrochemical catalytic performance of the single-atom catalyst of the present invention;
wherein, the liquid crystal display device comprises a liquid crystal display device,
FIG. 6a is CO 2 Electrocatalytic commercialized module structure diagram;
FIG. 6b is a full cell potential of a single-atom catalyst of the present invention at different currents in a commercialized module;
FIG. 6c is a graph of CO and H at different currents in a commercial module for a single-atom catalyst of the invention 2 Selectivity (1);
FIG. 6d shows CO and H at different currents in a commercial module for a single-atom catalyst according to the invention 2 Molar ratio;
fig. 6e is a long term stable operation of the single-atom catalyst of the present invention in a commercial module.
Detailed Description
In order to more clearly illustrate the technical aspects of the present invention, the following examples are set forth, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
The electroplating wastewater in the embodiment of the invention is obtained from a local electroplating plant, wherein the Ni content is 182.94mg/L, and the concentration of the rest heavy metals (mainly Cd, cu, fe, co, mn) is less than 5mg/L.
The activated carbon adsorbent in the embodiments of the present invention was purchased from a certain activated carbon factory in Guangzhou.
The biochar adsorbent in the embodiments of the present invention was purchased from forestry waste disposal company, while in huizhou.
The macroporous resin adsorbent in the embodiment of the invention is purchased from Shanghai environmental protection company.
The nitrogenous organic compound in the embodiment of the invention is urea and is purchased from a local agricultural product wholesale market.
Example 1
Waste adsorbent-based CO treatment method 2 The reduced monoatomic catalyst comprises monoatomic nickel, wherein the surface of the monoatomic nickel is covered with carbon nanotubes, the carbon nanotubes have a porous structure, and the diameter of the carbon nanotubes is 200nm.
The above waste adsorbent-based CO 2 Reduced monoatomic catalysisThe preparation method of the agent comprises the following steps:
s1, placing an activated carbon adsorbent in an adsorption column in an adsorption filter, and then taking electroplating wastewater containing Ni as raw water to flow into the adsorption column for adsorption filtration;
s2, adsorbing and regenerating the activated carbon adsorbent for multiple times until the concentration of Ni in the effluent is no longer changed, wherein the adsorbent cannot adsorb heavy metals at the moment, and a waste adsorbent is obtained;
s3, drying the waste adsorbent, mixing the waste adsorbent with a nitrogenous organic compound according to a mass ratio of 1:5, and then raising the temperature from room temperature to 550 ℃ at a heating rate of 2.5 ℃/min for 6 hours; then the temperature is increased from 550 ℃ to 1000 ℃ at the heating rate of 5 ℃/min, and the temperature is maintained at 1000 ℃ for 2 hours, and the product is obtained after natural cooling.
Fig. 1 shows a surface scanning electron microscope picture of the waste adsorbent in step S2.
Figure 2 shows the appearance of the monoatomic catalyst prepared in example 1.
Example 2
Waste adsorbent-based CO treatment method 2 The reduced monoatomic catalyst comprises monoatomic nickel, wherein the surface of the monoatomic nickel is covered with carbon nanotubes, the carbon nanotubes have a porous structure, and the diameter of the carbon nanotubes is 200nm.
The above waste adsorbent-based CO 2 A method for preparing a reduced monoatomic catalyst comprising the steps of:
s1, placing a macroporous resin adsorbent in an adsorption column in an adsorption filter tank, and then taking electroplating wastewater containing Ni as raw water to flow into the adsorption column for adsorption filtration;
s2, adsorbing and regenerating the macroporous resin adsorbent for multiple times until the concentration of Ni in the effluent is no longer changed, wherein the adsorbent cannot adsorb heavy metals at the moment, and a waste adsorbent is obtained;
s3, drying the waste adsorbent, mixing the waste adsorbent with a nitrogenous organic compound according to a mass ratio of 1:8, and then raising the temperature from room temperature to 550 ℃ at a heating rate of 2.5 ℃/min for 4 hours; then the temperature is increased from 550 ℃ to 1000 ℃ at the heating rate of 5 ℃/min, and the temperature is maintained at 1000 ℃ for 2 hours, and the product is obtained after natural cooling.
Example 3
Waste adsorbent-based CO treatment method 2 The reduced monoatomic catalyst comprises monoatomic nickel, wherein the surface of the monoatomic nickel is covered with carbon nanotubes, the carbon nanotubes have a porous structure, and the diameter of the carbon nanotubes is 200nm.
The above waste adsorbent-based CO 2 A method for preparing a reduced monoatomic catalyst comprising the steps of:
s1, placing a biochar adsorbent in an adsorption column in an adsorption filter tank, and then taking electroplating wastewater containing Ni as raw water to flow into the adsorption column for adsorption filtration;
s2, adsorbing and regenerating the biochar adsorbent for multiple times until the concentration of Ni in the effluent is no longer changed, wherein the adsorbent cannot adsorb heavy metals at the moment, and a waste adsorbent is obtained;
s3, drying the waste adsorbent, mixing the waste adsorbent with a nitrogenous organic compound according to a mass ratio of 1:10, and then heating the waste adsorbent from room temperature to 550 ℃ at a heating rate of 5 ℃/min for 4 hours; then the temperature is increased from 550 ℃ to 1000 ℃ at the heating rate of 5 ℃/min, and the temperature is maintained at 1000 ℃ for 2 hours, and the product is obtained after natural cooling.
Comparative example 1
A preparation method of the monoatomic catalyst comprises the following steps:
s1, performing anaerobic carbonization on a high-purity organic matter containing C at 1600 ℃ to obtain a carbon black substrate material with high graphitization degree;
s2, mixing the substrate material with an Au ion-containing solution (with the concentration of 0.5 wt%) to uniformly disperse the noble metal on the carbon substrate to obtain a precursor of the monoatomic catalyst;
s3, carbonizing the precursor again at the temperature of 1000 ℃ to obtain a product.
Comparative example 2
The difference between this comparative example and example 1 is that the nanoparticle catalyst based on the spent adsorbent: in step S3, no nitrogen-containing organic matter was added, and other materials and preparation methods were the same as in example 1.
Test example 1
The catalysts prepared in example 1 and comparative example were subjected to performance and morphology comparison, and the instruments used for the test include BET, scanning electron microscope, projection electron microscope, solid conductivity meter, spherical aberration correction transmission electron microscope, and the like.
The test results are as follows.
Table 1 comparison of performance parameters
| Project | Example 1 | Comparative example 1 | Comparative example 2 |
| Conductivity of | 7S/cm | 22S/cm | 5S/cm |
| Specific surface area | 570m 2 /g | 420m 2 /g | 130m 2 /g |
| CO 2 Adsorption capacity | 30cm 3 /g | 20cm 3 /g | 20cm 3 /g |
| Catalyst size | ＜1nm | ＜1nm | >100nm |
| Cost of | < 200 yuan/kg | 8-200 yuan/g | <200 yuan/kg |
FIG. 3 shows scanning electron micrographs of the nitrogen atom catalysts prepared in example 1 and comparative example 2;
wherein, the liquid crystal display device comprises a liquid crystal display device,
FIG. 3a is a scanning electron microscope image of the monoatomic catalyst prepared in example 1;
FIG. 3b is a single-atom-catalyst spherical aberration electron microscope image of example 1;
fig. 3c is a scanning electron microscope picture of the nanoparticle catalyst prepared in comparative example 2.
As shown in fig. 3a, after high-temperature carbonization, the heavy metal surface has a large number of carbon nanotubes generated, the diameter of the carbon nanotubes is about 200nm, the structure is fluffy and porous, which is favorable for monoatomic distribution of substances, and can provide a larger specific surface area for the catalyst, thereby promoting the promotion of catalytic efficiency. As shown in FIG. 3b, the carbonized waste adsorbent in example 1 has a large and uniform distribution of monoatomic Ni on the surface, and white bright spots, i.e., ni monoatoms, are uniformly distributed on the surface of biochar, so that agglomeration is not generated.
FIG. 4 shows the adsorption capacity of the monoatomic catalyst prepared in example 1;
wherein, the liquid crystal display device comprises a liquid crystal display device,
FIG. 4a is a BET and pore distribution of a monoatomic catalyst;
FIG. 4b CO for a monoatomic catalyst 2 Adsorption capacity.
FIG. 4 shows the specific surface area and CO of the Ni monoatomic catalyst prepared in example 1 2 Adsorption capacityIs a graph of the relationship of (1). From the results, the specific surface area of the catalyst is large (about 570 m) 2 And the misalignment between adsorption-desorption isotherms indicates that certain mesopores exist in the structure. In addition, CO 2 Adsorption isotherms indicate that the catalyst is CO 2 Excellent adsorption capacity, indicating that for CO 2 Has better affinity.
Test example 2
The monoatomic catalysts obtained in the examples and comparative examples were subjected to CO selectivity test comparison and other electrochemical tests. The testing method comprises the following steps: different potentials are applied or tested by cyclic voltammetry. The single-atom catalyst prepared in example 1 was applied to a commercial module and then subjected to electrochemical catalytic testing.
The results obtained are shown in Table 2.
Table 2 electrochemical test
| Material | Example 1 | Comparative example 1 | Comparative example 2 |
| CO optimum selectivity | 93.2％ | 90％ | <70％ |
| Electric double layer capacitor | 4.72mF/cm 2 | 2.56mF/cm 2 | 0.35mF/cm 2 |
From the above characterization data, it can be seen that the single-atom catalyst of example 1 has good selectivity compared to the commercial catalyst of comparative example 1, and similar catalytic effect to the commercial catalyst, the electric double layer capacitor and the electric double layer capacitor liquid of the commercial catalyst are on an order of magnitude. In combination, the gas diffusion electrode of the present invention can achieve even better performance than commercial products.
Figure 5 shows the selectivity of the single-atom catalysts prepared with different spent adsorbents for examples 1-3 and the nanoparticle catalysts prepared for comparative example 2 to electrocatalytic products.
FIG. 6 shows the electrochemical catalytic performance of the single-atom catalyst of the present invention;
wherein, the liquid crystal display device comprises a liquid crystal display device,
FIG. 6a is CO 2 Electrocatalytic commercialized module structure diagram;
FIG. 6b is a full cell potential of a single-atom catalyst of the present invention at different currents in a commercialized module;
FIG. 6c is a graph of CO and H at different currents in a commercial module for a single-atom catalyst of the invention 2 Selectivity of
FIG. 6d shows CO and H at different currents in a commercial module for a single-atom catalyst according to the invention 2 Molar ratio;
fig. 6e is a long term stable operation of the single-atom catalyst of the present invention in a commercial module.
When electrochemical catalysis is carried out, the monoatomic catalyst prepared by the invention can maintain Faraday Efficiency (FE) of more than 80 percent for CO in a relatively wide potential range, and H 2 The selectivity of the catalyst is less than 20%, which shows that the single-atom catalyst has extremely high selectivity to CO; the nanoparticle catalyst of comparative example 2 was a highly efficient hydrogen evolution catalyst (fig. 5). Directly in commercial modules for ECO 2 RR, it can still maintain 80% of FE of CO under 300mA of high current, and the corresponding full-cell potential difference is smaller, ensuring certain energy efficiency,thereby having a certain scale application prospect (figure 6).
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. Waste adsorbent-based CO treatment method 2 The reduced single-atom catalyst is characterized by comprising single-atom heavy metals, wherein the surfaces of the single-atom heavy metals are covered with carbon nanotubes, and the carbon nanotubes have porous structures.
2. Waste adsorbent based CO according to claim 1 2 Reduced monoatomic catalyst, characterized in that the heavy metal is selected from one or more of nickel, cadmium, copper, iron, cobalt, manganese, chromium, zinc, lead, antimony.
3. Waste adsorbent based CO according to claim 2 2 Reduced monoatomic catalyst, characterized in that the heavy metal is nickel.
4. Waste adsorbent based CO according to claim 1 2 Reduced monoatomic catalyst, characterized in thatThe diameter of the carbon nanotubes is 150-250nm.
5. Waste adsorbent based CO according to any one of claims 1-4 2 A method for preparing a reduced monoatomic catalyst comprising the steps of:
s1, adding a carbon-based adsorbent into an adsorption filter tank, and filtering electroplating wastewater containing heavy metals;
s2, adsorbing and regenerating the carbon-based adsorbent, and repeating for a plurality of times until the concentration of heavy metals in the wastewater is not changed any more to obtain a waste adsorbent;
s3, uniformly mixing the waste adsorbent and the nitrogenous organic matters, and then performing programmed heating carbonization to obtain the waste adsorbent-based CO used for the treatment of the waste adsorbent 2 Reduced monoatomic catalysts.
6. Waste adsorbent based CO according to claim 5 2 The preparation method of the reduced monoatomic catalyst is characterized in that the content of nickel element in the electroplating wastewater containing heavy metals is 150-250mg/L.
7. Waste adsorbent based CO according to claim 5 2 The preparation method of the reduced single-atom catalyst is characterized in that the carbon-based adsorbent is one or more selected from activated carbon, biochar and macroporous resin.
8. Waste adsorbent based CO according to claim 5 2 The preparation method of the reduced monoatomic catalyst is characterized in that the nitrogenous organic matters are selected from one or more of dicyandiamide, melamine, cyanuric chloride, urea and thiourea.
9. Waste adsorbent based CO according to claim 5 2 The preparation method of the reduced monoatomic catalyst is characterized in that in the step S3, the mass ratio of the waste adsorbent to the nitrogen-containing organic matter is 1 (5-10).
10. Waste adsorbent based CO according to claim 5 2 A method for preparing a reduced monoatomic catalyst, wherein in step S3, the programmed temperature is carbonized to: heating to 500-600deg.C at 2-5deg.C/min, and maintaining for 5-8 hr; heating to 900-1100 deg.C at 3-6deg.C/min, and maintaining for 2 hr.
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| CN112501637A (en) * | 2020-11-16 | 2021-03-16 | 河北工业大学 | Preparation method and application of non-noble metal modified nitrogenous biomass derived carbon |
| CN112675893A (en) * | 2020-12-31 | 2021-04-20 | 山东大学 | Method for preparing monatomic catalyst by using adsorbed-resolved waste adsorbent |
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| CN112501637A (en) * | 2020-11-16 | 2021-03-16 | 河北工业大学 | Preparation method and application of non-noble metal modified nitrogenous biomass derived carbon |
| CN112675893A (en) * | 2020-12-31 | 2021-04-20 | 山东大学 | Method for preparing monatomic catalyst by using adsorbed-resolved waste adsorbent |
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