WO2018111777A1 - Ingénierie de taille de pores de matériaux carbonés poreux à l'aide de structures organiques covalentes - Google Patents

Ingénierie de taille de pores de matériaux carbonés poreux à l'aide de structures organiques covalentes Download PDF

Info

Publication number
WO2018111777A1
WO2018111777A1 PCT/US2017/065627 US2017065627W WO2018111777A1 WO 2018111777 A1 WO2018111777 A1 WO 2018111777A1 US 2017065627 W US2017065627 W US 2017065627W WO 2018111777 A1 WO2018111777 A1 WO 2018111777A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbonaceous material
ctf
arene
monomer
covalent organic
Prior art date
Application number
PCT/US2017/065627
Other languages
English (en)
Inventor
Xiangfeng Duan
Chain Lee
Original Assignee
The Regents Of The University Of California
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Regents Of The University Of California filed Critical The Regents Of The University Of California
Publication of WO2018111777A1 publication Critical patent/WO2018111777A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065—Preparatory processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This disclosure generally relates to porous carbonaceous materials formed from covalent organic frameworks.
  • Oxygen Reduction Reaction is of importance for energy conversion technologies involving fuel cells, water splitting, and batteries.
  • Much efforts have been dedicated to the development of high performance transition metal-based catalyst as a cost- effective replacement of platinum on carbon (Pt/C).
  • Porous frameworks have been applied for the suspension of transition metal catalyst for ORR, many with performances comparable or even surpassing Pt/C.
  • Porous carbonaceous materials which are often nitrogen and metal doped, have been employed as a support for catalysts to facilitate their ORR activities.
  • Some embodiments of this disclosure are directed to a strategy of molecular tuning of monomers or precursors within porous frameworks to produce controlled pore size carbon-containing (or carbonaceous) materials.
  • control of pore size is attained by controlling a length of rigid molecules and using these as monomers or precursors for annealing into porous carbonaceous frameworks.
  • Rigid molecules encompass conjugated chemical species such as including aromatic hydrocarbons (e.g., benzene, biphenyl, triazine, pyridine, and other monocyclic or polycyclic arenes that may be substituted with cyano or other functional groups and including hetero forms thereof), alkenes (including one or more carbon-carbon double bonds), and alkynes (including one or more carbon-carbon triple bonds), and imines (including one or more carbon-nitrogen double bonds).
  • aromatic hydrocarbons e.g., benzene, biphenyl, triazine, pyridine, and other monocyclic or polycyclic arenes that may be substituted with cyano or other functional groups and including hetero forms thereof
  • alkenes including one or more carbon-carbon double bonds
  • alkynes including one or more carbon-carbon triple bonds
  • imines including one or more carbon-nitrogen double bonds
  • an approach of controlling pore size includes blending in sequentially longer monomers or precursors, along with a starting monomer of covalent triazine frameworks (CTFs), which produces CTFs with sequentially larger pore sizes. This is unlike other synthesis, which involves a single starting monomer.
  • CTFs covalent triazine frameworks
  • the approach can produce sequentially larger pore sized CTFs, and, after high temperature thermal annealing at about 700 °C to about 1000 °C, resulting carbonaceous materials retain their incrementally larger pores.
  • tuning of pores to different sizes can be attained to within several nanometers of each other.
  • the surface area to volume ratio of the materials can be adjusted by varying different monomers and blended monomer ratios.
  • Embodiments encompass other monomers or precursors beyond using cyano-containing or substituted molecules as precursors.
  • Molecular tuning can produce desirable materials for applications such as molecular and gas sieves, adsorbents, and electrodes.
  • the selectivity through molecular tuning can allow for investigation of optimum pore aperture, volume, and surface area to enhance performance for various applications which specify use of porous materials. This is especially significant in materials which should be electrically conductive, such as for fuel cells and batteries.
  • Fuel cell supports are affected by pore size. The supports can benefit from pore tunability, since they specify high surface area materials, which can deliver maximum mass transfer of reactant to a catalytic interface. Battery cathodes and anodes also can benefit from tunable porous carbonaceous materials since they rely on conducting high surface area materials.
  • Supercapacitors rely on conductivity and surface area. However, accessibility of an usable surface area may pose a challenge. Molecular tuning can enhance and optimize porous carbonaceous materials for high performance supercapacitors.
  • FIG. 1 Schematic representation of the synthesis of cobalt- chelated covalent triazine frameworks (Co-CTFs) with different pore sizes. The strategy of creating sequentially longer trimered units from the synthesis of CTFs using a single monomer, and mixed monomers are displayed. The cubes represent different Co-CTFs and their enhanced pore size.
  • Co-CTFs cobalt- chelated covalent triazine frameworks
  • FIG. 1 Pore size characterization, (a) N 2 Brunauer-Emmett-Teller (BET) isotherms, (b) Differential pore volume overlays of Co-CTFs. (c) Bar graph of specific surface areas corresponding to each size pore, (d) Double layer capacitance slope comparisons of Co-CTF-S, -M, and -L are illustrated. Corresponding electrochemical surface area (ECSA) calculated and listed according to Co-CTFs.
  • BET Brunauer-Emmett-Teller
  • ECSA electrochemical surface area
  • Figure 3 Cumulative pore volumes of Co-CTF-S (lower curve), -M (middle curve), and -L (top curve).
  • FIG. 1 Electrochemical Performance, (a) Overlay of different Co-CTF linear scan voltammetry (LSV) curves measured at about 1600 r.p.m. in about 0.1 M KOH. Labels indicate pores sizes small (S), medium (M) and large (L). (b) Kinetic current density and Ei /2 on the y-axes, plotted against different pore sizes on the x-axis. (c) Nyquist plot overlays of Co-CTFs.
  • LSV linear scan voltammetry
  • FIG. 7 Active catalyst evaluation, (a) Powder X-ray diffraction (PXRD) overlay of Co-CTF-L before and after acid etching, (b) LSV overlay of Co-CTF-L before and after acid etching in about 0.1 M KOH electrolyte. Labels represent Co-CTF-L, and post acid etching of Co-CTF-L for Figures 7(a) and (b). (c) and (d) Images of Co-CTF-L.
  • PXRD Powder X-ray diffraction
  • Figure 9 X-ray photoelectron spectroscopy (XPS) data of survey and nitrogen of Co-CTF-L.
  • FIG. 10 XPS Spectrum of Cobalt 2p of Co-CTF-L.
  • Figure 11 Electron imaging of Co-CTF-L.
  • HAADF-STEM High angle annular dark field scanning transmission electron microscopy
  • Scale bars are 200 nm (a), 100 nm (b), 5 nm (c), and 1 nm (d).
  • Figure 14 DFT differential pore volume measurements of a same sample, CTF-L, after about 400 °C sublimation and about 900 °C annealing.
  • Figure 15 Additional molecular tuning pore size measurements using DFT calculations from BET measurements.
  • Figure 16 Scheme 2 - Trimerization of 4,4'-biphenyl dicyanobenzene (BPDC) into a triazine polymer. Upon metal chelation and annealing, the structure becomes disordered and includes cobalt particles. Images of the transition from polymer, to metal chelation, and annealed material are displayed.
  • BPDC 4,4'-biphenyl dicyanobenzene
  • Figure 17. (a) Low magnification TEM image of Co-CTF. (b) Scanning electron microscopy (SEM) image of Co-CTF, showing large cavernous pores, (c). High resolution TEM (HRTEM) image of graphitically wrapped cobalt nanoparticle. (d) BET nitrogen isotherm of Co-CTF. Curve with squares represents absorption, and curve with circles represents desorption. (e) I-V curve performed on bulk sample of Co-CTF.
  • Figure 18 (a) EDX mapping of Co-CTF. (b) XPS survey spectrum of Co- CTF. (c) Nitrogen Is spectrum displays different types of nitrogen bonding, (d) Cobalt 2p spectrum displays cobalt ion peaks.
  • Figure 19 (a) Different LSV curves of Co-CTF in both acidic and basic electrolytes, along with Pt/C as a comparison, (b) Rotating ring-disk electrode (RRDE) measurements in both acidic and basic electrolytes displaying LSV and peroxide currents at different rotation speeds, (c) Stability measurements plotted by number of cycles along with change in current, (d) Electron transfer numbers bar graph of Co-CTF in both acidic and basic electrolytes, with Pt/C as a comparison. [0034] Figure 20. (a) LSV of Co-CTF, along with stability after 2000 cycles. Pt/C added for comparison, (b) Comparison chart of different transition metal-based F£ER catalysts along with Co-CTF.
  • RRDE Rotating ring-disk electrode
  • CTFs Covalent triazine frameworks
  • COFs covalent organic frameworks
  • the streamlined synthetic approach overcomes multiple difficulties of producing high porosity: (i) avoiding tedious organic synthesis techniques, (ii) maintaining full conjugation, and (iii) ability to bind transition metals.
  • Tuning the pore sizes of CTFs, and using them as precursors for annealing, resulted in three robust frameworks which maintained sequentially higher specific surface areas, and also successively increased electrochemical surface areas.
  • evaluation is made of the progressive pore tuning, and report is made of their correlation to oxygen reduction behavior in alkaline electrolyte. It is found that the largest pore size supported electrocatalyst, Co- CTF -L, has exceptional ORR performance, with half-wave over-potential of about 38 mV lower than that of commercial Pt/C.
  • Cobalt chelation to the CTFs was performed by submerging the material in a CoCl 2 /ethanol solution (about 1 mg/mL) for about 24 h. A visible de-coloration of the metal solution could be observed, after which the CTFs were washed several times with ethanol, removing any excess non-chelated cobalt.
  • the CTFs were annealed at about 900 °C for about 2 h in about 90: 10 mixture of Ar:H 2 for all samples.
  • the pyrolized materials are noted in relation to their pore size of small (Co-CTF-S), medium (Co-CTF-M), and large (Co-CTF-L).
  • the treatment temperature of about 900 °C performs well with the material in terms of ORR.
  • Pore size evaluations began with using N 2 adsorption techniques for each material.
  • the corresponding surface areas were determined through Brunauer-Emmett-Teller (BET) analysis to be about 425, about 780, about 1480 m 2 g "1 for Co-CTF-S, Co-CTF-M, and Co-CTF-L respectively ( Figure 2a).
  • BET Brunauer-Emmett-Teller
  • the isotherm shapes of Co-CTF-M and Co-CTF-L are type-IV, which contain a typical hysteresis loop due to nitrogen fragility artifact during mesopore desorption.
  • the C d i capacitance from CV progress from about 5.5 mF cm “2 , to about 31 mF cm “2 , and finally about 49 mF cm “2 as pores expand, a near 10-fold increase.
  • These C d i measurements translate into specific capacitances of about 14 F g "1 , about 78 F g "1 , and about 122 F g “1 respectively.
  • C d i values can be computed into ECSA's of about 60 m 2 g “1 , to about 380 m 2 g “1 , reaching about 606 m 2 g “1 respectively, shown in Figure 2d.
  • the experiments demonstrate that pore tuning of Co-CTFs increase surface area, and also C d i and ECSA. These factors play major roles for oxygen reduction by aiding in: reactant delivery, access of surfaces for catalysis, ionic conduction, and product removal from pores.
  • FIG. 5a overlays the linear scan voltammetry (LSV) curves of the three Co-CTF samples with different pore sizes. As pore size increases, a significant enhancement of both kinetic slope and the diffusion limiting current can be achieved. Calculated kinetic current densities and Ei /2 wave potentials are plotted against the respective Co-CTFs in Figure 5b. Improving kinetic performance can be attributed to four major ways: decreasing the activation barrier, increasing the temperature, increasing the reactant concentration, and increasing the number of possible reaction sites. The kinetic improvements can be accredited to the latter two: a greater rate of exchange between reactant and product, and also an increase in accessibility to catalytic sites, both originating from pore size engineering.
  • a representative CV curve of Co-CTF-L is displayed in Figure 5d. Cyclic scans of N 2 saturated KOH solution show the absence of the characteristic ORR cathodic peak. Upon 0 2 electrolyte saturation a strong peak at about 0.86 V appears. The ORR activity of the Co-CTF-L sample is further compared with an about 20 wt.% Pt/C. As shown in Figure 5e, a steep kinetic slope is induced by the large pore size and results in an impressive Ei/2 of Co-CTF-L that is about 38 mV less than that of Pt/C (about 0.87 V versus about 0.83 V in Figure 5e).
  • Figure 5f displays Koutecky-Levich (K-L) plot of Co-CTF-L.
  • the linearity indicates first order rate kinetics, which aligns well with electron transfer number (n) of about 3.98 measured through peroxide current on a rotating ring-disk electrode (RRDE) in Figure 6. This is very close in line with commercial Pt/C, which has theoretical n of about 4.0.
  • Co-CTF samples were treated with about 0.5 M H 2 S0 4 in order to dissolve away most of the large cobalt particles and unstable atoms. Comparing the post acid treated material with powder X-ray diffraction (PXRD) analysis in Figure 7a reveals most of the cobalt has been removed; yet the ORR performance improves. The weak signal signifies the significantly reduced content, and the peak broadness is indicative of small particles. LSV curves measured for the post acid treatment gave a slight improvement in overall performance, resulting in higher diffusion limiting current especially at about 0.76 V in Figure 7b. These results indicate that the active ORR species in the Co-CTFs are not the large particles but likely small clusters and possibly atomic cobalt species.
  • PXRD powder X-ray diffraction
  • Cobalt 2p spectrums in Figure 10 designate uniform bands at about 781.1 and about 796.2 eV corresponding to Co 2p 3/2 and Co 2pi /2 , for the three Co-CTFs .
  • the non-observance of cobalt metal may be attributed to the sampling depth of XPS.
  • the specific form of cobalt in ORR catalyst remains to be confirmed, whether it is large particles, small clusters, or single atoms. It is possible that in transition metal-nitrogen- carbon systems, the main contribution in electrochemistry comes from small clusters and single atoms, which is the case for iron-nitrogen-carbon ORR catalysts.
  • TEM image in Figure 11a displays the presence of graphitic ribbons, amongst the CTF, along with remaining cobalt particles that were not etched away. Elemental maps of carbon, nitrogen, and cobalt were obtained through energy dispersive X-ray (EDX) analysis under high resolution TEM (URTEM) ( Figure 1 lb). To investigate the presence of smaller clusters and possible single atoms, an aberration corrected High Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF-STEM) is used under dark field imaging ( Figure 11c). An atomic resolution image of a sub-5 nm cobalt particle is captured in Figure l id.
  • HAADF-STEM High Angle Annular Dark Field Scanning Transmission Electron Microscopy
  • the highly crystalline Co 0 particles are confirmed by (111) facet with d-spacing of about 2.2 A, which correlates well with the PXRD in Figure 7. It should be noted that a low accelerating voltage of about 80 kV was used to avoid electro-beam induced damage of the CTF and clusters.
  • the molecular tuning strategy is investigated by changing the ratios of blended monomers.
  • increasing the amount of BPDC, a longer linker than DCP results in the pore stretching.
  • the cavity opening is mainly prevalent in the about 5-12 nm range as observed from the differential volume graph of Figure 13. A slight reduction in pore volume between about 2 to 5 nm is also measured.
  • Figure 15 displays the DFT differential pore volume distributions of 4 different CTFs, from size 'M', along with varied stoichiometric ratios of size 'L' and lastly BPDC. The incremental pore expansion holds true for all 4 compounds.
  • BPDC being the longest monomer, and when used solely as the starting material, produces a highly mesoporous CTF.
  • a method of forming a porous carbonaceous material includes: (1) providing at least two different monomers; (2) polymerizing the monomers to form a covalent organic framework; and (3) heating the covalent organic framework to form the carbonaceous material.
  • the at least two different monomers have different molecular weights. In some embodiments, the at least two different monomers have different molecular lengths along their longest dimensions.
  • a first monomer of the monomers is a N-heterocyclic arene.
  • the N-heterocyclic arene includes a 6-membered ring structure.
  • the N-heterocyclic arene is a pyridine.
  • the N-heterocyclic arene or the pyridine is substituted with at least one functional group configured to form a covalent linkage with a corresponding functional group.
  • the N-heterocyclic arene or the pyridine is substituted with at least one cyano group.
  • the first monomer is 2,6- dicyanopyridine.
  • the first monomer is represented by a chemical formula:
  • a second monomer of the monomers is an arene.
  • the arene includes a 6-membered ring structure.
  • the arene is devoid of nitrogen in its ring structure.
  • the arene includes two or more 6-membered ring structures that are bonded to one another.
  • the arene is a benzene.
  • the arene is a biphenyl.
  • the arene is a triphenyl (e.g., /?ara-triphenyl) or a higher order phenyl.
  • the arene is substituted with at least one functional group configured to form a covalent linkage with a corresponding functional group.
  • the arene is substituted with at least one cyano group.
  • Other functional groups include an amide group, a boronic acid group, a boronic ester group, a borosilicate group, an amine group, an aldehyde group, a hydrazine group, and a hydrazide group.
  • the second monomer is 1,4-dicyanobenzene or 4,4' -biphenyl dicarbonitrile.
  • the second monomer is represented by a chemical formula:
  • R" and R" are cyano groups, or can be independently selected from other functional groups listed above, and n is an integer that is 1, 2, 3, or greater.
  • a molar ratio of the first monomer to the second monomer is in a range of about 1 : 15 to about 2: 1, such as about 1 : 10 to about 1 : 1, about 1 :8 to about 1 : 1, about 1 :6 to about 1 : 1, about 1 :4 to about 1 : 1, or about 1 :2 to about 1 : 1.
  • the molar ratio of the first monomer to the second monomer is about 1 : 1 or less than about 1 : 1.
  • polymerizing the monomers is performed in the presence of a catalyst, such as zinc chloride.
  • polymerizing the monomers includes heating at a temperature in a range of about 250 °C to about 550 °C, about 300 °C to about 500 °C, or about 400 °C for a time duration in a range of about 20 h to about 60 h, about 30 h to about 50 h, or about 40 h.
  • polymerizing the monomers includes forming covalent linkages between the monomers.
  • polymerizing the monomers includes forming triazine moieties.
  • the triazine moieties are bonded to one another via linkers.
  • the linkers are represented by a chemical formula:
  • n is an integer that is 1, 2, 3, or greater.
  • heating the covalent organic framework is performed at a temperature in a range of about 700 °C to about 1000 °C, about 800 °C to about 1000 °C, or about 900 °C for a time duration in a range of about 0.5 h to about 5 h, about 1 h to about 3 h, or about 2 h.
  • the method includes, prior to heating the covalent organic framework, exposing the covalent organic framework to a solution of a metal salt.
  • the metal salt includes a transition metal.
  • the transition metal is cobalt.
  • heating the covalent organic framework includes forming the carbonaceous material including the transition metal incorporated therein.
  • the transition metal incorporated in the carbonaceous material is in the form of nanoparticles, such as having sizes in a range of about 1 nm to about 100 nm, about 1 nm to about 80 nm, about 1 nm to about 60 nm, about 1 nm to about 40 nm, about 1 nm to about 20 nm, about 1 nm to about 10 nm, or about 1 nm to about 5 nm.
  • the transition metal incorporated in the carbonaceous material is in the form of atomic species.
  • a method of forming a porous carbonaceous material includes: (1) providing a monomer; (2) polymerizing the monomer to form a covalent organic framework; (3) exposing the covalent organic framework to a solution of a transition metal; and (4) heating the covalent organic framework to form the carbonaceous material incorporating the transition metal.
  • a monomer is an arene.
  • the arene includes a 6-membered ring structure.
  • the arene is devoid of nitrogen in its ring structure.
  • the arene includes two or more 6-membered ring structures that are bonded to one another.
  • the arene is a benzene.
  • the arene is a biphenyl.
  • the arene is a triphenyl (e.g., ?ara-triphenyl) or a higher order phenyl.
  • the arene is substituted with at least one functional group configured to form a covalent linkage with a corresponding functional group. In some embodiments, the arene is substituted with at least one cyano group.
  • Other functional groups include an amide group, a boronic acid group, a boronic ester group, a borosilicate group, an amine group, an aldehyde group, a hydrazine group, and a hydrazide group.
  • the monomer is 1,4- dicyanobenzene or 4,4' -biphenyl dicarbonitrile. In some embodiments, the monomer is represented by a chemical formula:
  • R" and R" are cyano groups, or can be independently selected from other functional groups listed above, and n is an integer that is 1, 2, 3, or greater.
  • polymerizing the monomer is performed in the presence of a catalyst, such as zinc chloride.
  • polymerizing the monomer includes heating at a temperature in a range of about 250 °C to about 550 °C, about 300 °C to about 500 °C, or about 400 °C for a time duration in a range of about 20 h to about 60 h, about 30 h to about 50 h, or about 40 h.
  • polymerizing the monomer includes forming covalent linkages between molecules of the monomer.
  • polymerizing the monomer includes forming triazine moieties.
  • the triazine moieties are bonded to one another via linkers.
  • the linkers are represented by a chemical formula:
  • n is an integer that is 1, 2, 3, or greater.
  • the transition metal is cobalt.
  • the transition metal incorporated in the carbonaceous material is in the form of nanoparticles, such as having sizes in a range of about 1 nm to about 100 nm, about 1 nm to about 80 nm, about 1 nm to about 60 nm, about 1 nm to about 40 nm, about 1 nm to about 20 nm, about 1 nm to about 10 nm, or about 1 nm to about 5 nm.
  • the transition metal incorporated in the carbonaceous material is in the form of atomic species.
  • heating the covalent organic framework is performed at a temperature in a range of about 700 °C to about 1000 °C, about 800 °C to about 1000 °C, or about 900 °C for a time duration in a range of about 0.5 h to about 5 h, about 1 h to about 3 h, or about 2 h.
  • a resulting carbonaceous material has a surface area of about 400 m 2 g "1 or greater, about 500 m 2 g "1 or greater, about 600 m 2 g "1 or greater, about
  • pores of the carbonaceous material having sizes in a range of about 1 nm to about 20 nm account for at least 90% of a total pore volume within the carbonaceous material.
  • pores of the carbonaceous material having sizes in a range of about 1 nm to about 12 nm account for at least 90% of a total pore volume within the carbonaceous material.
  • pores of the carbonaceous material having sizes in a range of about 1 nm to about 8 nm account for at least 90% of a total pore volume within the carbonaceous material.
  • pores of the carbonaceous material having sizes in a range of about 1 nm to about 5 nm account for at least 90% of a total pore volume within the carbonaceous material. In some embodiments, pores of the carbonaceous material having sizes in a range of about 1 nm to about 3 nm account for at least 90% of a total pore volume within the carbonaceous material.
  • a total pore volume within the carbonaceous material is about 0.2 cm 3 g "1 or greater, about 0.3 cm 3 g “1 or greater, about 0.4 cm 3 g “1 or greater, about 0.5 cm 3 g “1 or greater, about 0.6 cm 3 g “1 or greater, about 0.7 cm 3 g “1 or greater, or about 0.8 cm 3 g “1 or greater, and up to about 0.9 cm 3 g "1 or greater.
  • an electrical conductivity of the carbonaceous material is about 2 S/cm or greater, about 4 S/cm or greater, about 6 S/cm or greater, about 8 S/cm or greater, about 10 S/cm or greater, about 12 S/cm or greater, about 14 S/cm or greater, about 16 S/cm or greater, or about 18 S/cm or greater, and up to about 20 S/cm or greater.
  • the carbonaceous material includes carbon and nitrogen, and an atomic percentage of nitrogen within the carbonaceous material is about 2% or greater, about 4% or greater, about 6% or greater, about 8% or greater, or about 10% or greater, and up to about 12% or greater.
  • the carbonaceous material includes carbon, nitrogen, and a transition metal, and an atomic percentage of the transition metal within the carbonaceous material is about 2% or greater, about 4% or greater, about 6% or greater, about 8% or greater, or about 10% or greater, and up to about 11% or greater.
  • CTF-S 2,6-dicyanopyridine (DCP) was mixed in an about 1 : 1 molar ratio with anhydrous ZnCl 2 (about 2 grams total weight) and flame sealed in a quartz tube. The tube was placed in a furnace at about 400 °C for about 40 h, where the CTF was then washed with copious amounts of about 1.0 M HC1, tetrahydrofuran (TUF), and acetone.
  • DCP 2,6-dicyanopyridine
  • CTF-M Monomers in about 1 :2 molar mixture of DCP and 1,4- dicyanobenzene (DCB), along with a substantially equal molar amount of anhydrous ZnCl 2 , were flame sealed in a quartz tube and followed the same post-synthesis procedure above.
  • CTF-L Monomers in about 1 :2 molar mixture of DCP and 4,4'-biphenyl dicyanobenzene (BPDC), along with a substantially equal molar amount of anhydrous ZnCl 2 , were flame sealed in a quartz tube and followed the same post-synthesis procedure above.
  • DCB 1,4- dicyanobenzene
  • BPDC 4,4'-biphenyl dicyanobenzene
  • TEM TEM T12 Quick CryoEM
  • HRTEM was performed using a Titan at about 300 kV accelerating voltage.
  • Scanning electron microscopy (Zeiss Supra 40VP) was used to evaluate the morphology of the Co-CTFs.
  • XRD was carried out using a Bruker D8 X- ray Powder Diffractometer with Cu Ka radiation.
  • BET isotherms and pore size data were measured using a Miromeritics Tristar II 3020.
  • XPS Azis Ultra DLD
  • TGA Thermogravimetric analysis
  • an electrolyzer stores energy by splitting water into H 2 and 0 2 , and a fuel cell converts the chemical energy into electrical energy.
  • a fuel cell converts the chemical energy into electrical energy.
  • URFC unified regenerative fuel cell
  • a single module serves the dual purposes of electrolyzer and fuel cell, where the module utilizes bi-functional catalysts for both electrolysis and energy conversion. This design efficiency saves components, and also material, space, and costs.
  • CTFs can be desirable platforms for electrocatalysts. However, to obtain good electrochemical performance, blending with carbon is performed due to their low conductivities. Though this is a solution, this has the added effect of lowering the number of active catalyst per area and weight.
  • synthesis is performed of Co-CTF, a cobalt-loaded CTF-derived material formed from super-acid polymerized triazine films. The resultant polymer when immersed into a cobalt solution can strongly chelate the metal. After high temperature annealing, the resultant Co-CTF possess desired electrochemical properties of: intrinsic conductivity, high surface area, nitrogen doping, and transition metal binding.
  • the CTF and cobalt play synergistic roles for each other.
  • Cobalt aids in the graphitization of the CTF, allowing the framework to achieve metallic-like conductivities, as well as remaining an active catalyst to enhance ORR and HER.
  • the CTF upon graphitization now acts as a desirable electrocatalytic support, aiding the cobalt with surface area, diffusion, and electron transport across a three-dimensional (3D) framework.
  • Co-CTF was formed using metal binding followed by high-temperature treatment (Scheme 2 in Figure 16).
  • Polymerized CTF was prepared and was immersed into a cobalt chloride and ethanol solution at about 60 °C overnight, allowing for metal chelation. The CTF turned blue, indicating metal binding.
  • the sample was washed with ethanol to remove any excess cobalt then annealed under Ar and H 2 gas at about 900 °C for about 2 h. Other annealing temperatures of about 700, about 800, and about 1000 were tested; however, about 900 °C yielded the highest ORR performance. So for further discussion, unless stated otherwise in this example, all samples were treated under about 900 °C temperature. Of note, this allows CTFs to be synthesized from super-acid and is able to absorb metal atoms from solution. This finding may lead to further applications of super-acid CTFs in membrane purifications.
  • Nitrogen absorption analysis gave a specific surface area of about 560 m 2 /g as seen in Figure 17d.
  • a typical type I-V isotherm was observed, which is a characteristic of mesoporous materials (Figure 17e).
  • measurement is made of a bulk centimeter- sized sample using vapor deposited gold electrodes.
  • a conductivity of about 20 S/cm is obtained at room temperature, which places Co-CTF amongst the best organic conductors.
  • the presence of cobalt NCs aided in the graphitization and therefore conductivity enhancement, since non-cobalt thermally annealed CTFs gave a lower conductivity of about 1 x 10 "3 S/cm.
  • Co-CTF begins F£ER at an onset potential of about 70 mV as seen in the polarization curves of Figure 20a, overlaid with Pt/C standard whose onset is near zero. At about 10 mA of current density, Co-CTF operates at just about 200 mV overpotential.
  • a conductive 3D framework which includes transition metal cobalt and performs two electrocatalytic reactions, ORR and TIER with good performance.
  • the framework, Co-CTF includes a wide range of pores, ranging from micro- to mesoporous, many are large enough to be observed under SEM. This translates into highly accessible surface area, which optimizes diffusion attributing to Co- CTF's high performance.
  • the results show the synergistic behavior between CTF and cobalt, where they complement each other in a thermal reaction to produce conductive 3D materials, and whose applications may be utilized in sensing, devices, and batteries.
  • the bi-functional catalyst advances the applicability of CTFs as supports for water splitting and fuel cell applications.
  • a set refers to a collection of one or more objects.
  • a set of objects can include a single object or multiple objects.
  • connection refers to an operational coupling or linking.
  • Connected objects can be directly coupled to one another or can be indirectly coupled to one another, such as via one or more other objects.
  • a size of an object that is circular or spherical can refer to a diameter of the object.
  • a size of the object can refer to a diameter of a corresponding circular or spherical object, where the corresponding circular or spherical object exhibits or has a particular set of derivable or measurable properties that are substantially the same as those of the non-circular or non- spherical object.
  • the objects can have a distribution of sizes around the particular size.
  • a size of a set of objects can refer to a typical size of a distribution of sizes, such as an average size, a median size, or a peak size.
  • the terms “substantially” and “about” are used to describe and account for small variations.
  • the terms can refer to instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs to a close approximation.
  • the terms can refer to a range of variation of less than or equal to ⁇ 10% of that numerical value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to ⁇ 2%, less than or equal to ⁇ 1%), less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
  • concentrations, amounts, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity and should be understood flexibly to include numerical values explicitly specified as limits of a range, but also to include all individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly specified. For example, a range of about 1 to about 200 should be understood to include the explicitly recited limits of about 1 and about 200, but also to include individual values such as about 2, about 3, and about 4, and sub-ranges such as about 10 to about 50, about 20 to about 100, and so forth.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

Un procédé de formation d'un matériau carboné poreux comprend : (1) la fourniture d'au moins deux monomères différents; (2) la polymérisation des monomères pour former une structure organique covalente; et (3) le chauffage de la structure organique covalente pour former le matériau carboné.
PCT/US2017/065627 2016-12-12 2017-12-11 Ingénierie de taille de pores de matériaux carbonés poreux à l'aide de structures organiques covalentes WO2018111777A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662433149P 2016-12-12 2016-12-12
US62/433,149 2016-12-12

Publications (1)

Publication Number Publication Date
WO2018111777A1 true WO2018111777A1 (fr) 2018-06-21

Family

ID=62559203

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2017/065627 WO2018111777A1 (fr) 2016-12-12 2017-12-11 Ingénierie de taille de pores de matériaux carbonés poreux à l'aide de structures organiques covalentes

Country Status (1)

Country Link
WO (1) WO2018111777A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109499600A (zh) * 2018-12-14 2019-03-22 江苏科技大学 一种双金属氮掺杂碳/二硫化钼复合电催化剂材料、制备方法及其应用
CN110183676A (zh) * 2019-05-31 2019-08-30 上海交通大学 一种全共轭碳碳双键连接的富氮共价有机框架材料的制备方法
CN110479379A (zh) * 2019-08-28 2019-11-22 浙江工业大学 一种基于负载Ru纳米颗粒的共价有机框架材料催化剂及其制备方法和应用
JP2020040857A (ja) * 2018-09-12 2020-03-19 星和電機株式会社 共有結合性有機構造体の焼成体およびその製造方法
CN111548487A (zh) * 2020-05-13 2020-08-18 广州大学 一种孔状有机聚合物及其制备方法与应用
CN111604039A (zh) * 2020-05-26 2020-09-01 首都师范大学 一种三维共价有机骨架材料、开管毛细管电色谱柱及制备方法
CN112038647A (zh) * 2020-08-31 2020-12-04 江南大学 一种基于COFs衍生纳米碳管催化ORR反应的方法
CN114736370A (zh) * 2022-04-25 2022-07-12 吉林师范大学 氟掺杂的共价三嗪骨架聚合物及其含硫复合物，以及制备方法和应用
CN116914124A (zh) * 2023-09-12 2023-10-20 深圳华钠新材有限责任公司 一种具有共价有机框架的层状氧化物正极材料及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4775655A (en) * 1985-11-18 1988-10-04 Internationale Octrooi Maatschappij "Octropa" Porous carbon structures and methods for their preparation
US20030219640A1 (en) * 2002-01-23 2003-11-27 Polyfuel, Inc. Acid-base proton conducting polymer blend membrane
US20100280216A1 (en) * 2007-06-15 2010-11-04 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. Method of preparing organic porous solids and solids obtainable by this method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4775655A (en) * 1985-11-18 1988-10-04 Internationale Octrooi Maatschappij "Octropa" Porous carbon structures and methods for their preparation
US20030219640A1 (en) * 2002-01-23 2003-11-27 Polyfuel, Inc. Acid-base proton conducting polymer blend membrane
US20100280216A1 (en) * 2007-06-15 2010-11-04 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. Method of preparing organic porous solids and solids obtainable by this method

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
KAMIYA, K ET AL.: "Platinum-modified covalent triazine frameworks hybridized with carbon nanoparticles as methanol-tolerant oxygen reduction electrocatalysts", NATURE COMMUNICATIONS, vol. 5, no. 1, 22 September 2014 (2014-09-22), pages 1 - 6, XP055493219 *
LIU, J ET AL.: "A facile soft-template synthesis of mesoporous polymeric and carbonaceous nanospheres", NATURE COMMUNICATIONS, vol. 4, no. 1, 17 December 2013 (2013-12-17), pages 1 - 7, XP055493184 *
YANG, Y ET AL.: "The Correlation of Interfacial Interaction and Catalytic Performance of N-Doped Mesoporous Carbon Supported Cobalt Nanoparticles for Fischer-Tropsch Synthesis", THE JOURNAL OF PHYSICAL CHEMISTRY C, vol. 188, no. 1, 9 December 2013 (2013-12-09), pages 269 - 277, XP055493203 *
ZHU, X ET AL.: "Synthesis of Porous, Nitrogen-Doped Adsorption/Diffusion Carbonaceous Membranes for Efficient C02 Separation", MACROMOLECULAR RAPID COMMUNICATIONS, vol. 34, 3 March 2013 (2013-03-03), pages 452 - 459, XP055493198 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020040857A (ja) * 2018-09-12 2020-03-19 星和電機株式会社 共有結合性有機構造体の焼成体およびその製造方法
CN109499600A (zh) * 2018-12-14 2019-03-22 江苏科技大学 一种双金属氮掺杂碳/二硫化钼复合电催化剂材料、制备方法及其应用
CN110183676A (zh) * 2019-05-31 2019-08-30 上海交通大学 一种全共轭碳碳双键连接的富氮共价有机框架材料的制备方法
CN110183676B (zh) * 2019-05-31 2021-07-13 上海交通大学 一种全共轭碳碳双键连接的富氮共价有机框架材料的制备方法
CN110479379B (zh) * 2019-08-28 2022-07-22 浙江工业大学 一种基于负载Ru纳米颗粒的共价有机框架材料催化剂及其制备方法和应用
CN110479379A (zh) * 2019-08-28 2019-11-22 浙江工业大学 一种基于负载Ru纳米颗粒的共价有机框架材料催化剂及其制备方法和应用
CN111548487A (zh) * 2020-05-13 2020-08-18 广州大学 一种孔状有机聚合物及其制备方法与应用
CN111548487B (zh) * 2020-05-13 2022-08-30 广州大学 一种孔状有机聚合物及其制备方法与应用
CN111604039A (zh) * 2020-05-26 2020-09-01 首都师范大学 一种三维共价有机骨架材料、开管毛细管电色谱柱及制备方法
CN111604039B (zh) * 2020-05-26 2023-05-23 首都师范大学 一种三维共价有机骨架材料、开管毛细管电色谱柱及制备方法
CN112038647A (zh) * 2020-08-31 2020-12-04 江南大学 一种基于COFs衍生纳米碳管催化ORR反应的方法
CN112038647B (zh) * 2020-08-31 2021-07-27 江南大学 一种基于COFs衍生纳米碳管催化ORR反应的方法
CN114736370A (zh) * 2022-04-25 2022-07-12 吉林师范大学 氟掺杂的共价三嗪骨架聚合物及其含硫复合物，以及制备方法和应用
CN116914124A (zh) * 2023-09-12 2023-10-20 深圳华钠新材有限责任公司 一种具有共价有机框架的层状氧化物正极材料及制备方法
CN116914124B (zh) * 2023-09-12 2023-12-01 深圳华钠新材有限责任公司 一种具有共价有机框架的层状氧化物正极材料及制备方法

Similar Documents

Publication Publication Date Title
WO2018111777A1 (fr) Ingénierie de taille de pores de matériaux carbonés poreux à l'aide de structures organiques covalentes
Tavakkoli et al. Mesoporous single-atom-doped graphene–carbon nanotube hybrid: Synthesis and tunable electrocatalytic activity for oxygen evolution and reduction reactions
Song et al. Zn3 [Fe (CN) 6] 2 derived Fe/Fe5C2@ N-doped carbon as a highly effective oxygen reduction reaction catalyst for zinc-air battery
Guo et al. CoMo carbide/nitride from bimetallic MOF precursors for enhanced OER performance
Gu et al. Facile synthesis of N-doped graphene-like carbon nanoflakes as efficient and stable electrocatalysts for the oxygen reduction reaction
Chen et al. Ultrasonic plasma engineering toward facile synthesis of single-atom MN 4/N-doped carbon (M= Fe, Co) as superior oxygen electrocatalyst in rechargeable zinc–air batteries
Hou et al. Vertically oriented cobalt selenide/NiFe layered-double-hydroxide nanosheets supported on exfoliated graphene foil: an efficient 3D electrode for overall water splitting
Zhang et al. Nitrogen-doped carbon encapsulating γ-MoC/Ni heterostructures for efficient oxygen evolution electrocatalysts
US10170770B2 (en) N-doped porous carbon electrocatalyst and process for preparation thereof
Qian et al. Direct growth of NiCo 2 O 4 nanostructures on conductive substrates with enhanced electrocatalytic activity and stability for methanol oxidation
Huang et al. Self-transforming ultrathin α-Co (OH) 2 nanosheet arrays from metal-organic framework modified graphene oxide with sandwichlike structure for efficient electrocatalytic oxygen evolution
Zhu et al. Biochemistry-inspired direct synthesis of nitrogen and phosphorus dual-doped microporous carbon spheres for enhanced electrocatalysis
Yang et al. Self‐Assembly of Three‐Dimensional Zinc‐Doped NiCo2O4 as Efficient Electrocatalysts for Oxygen Evolution Reaction
Lin et al. Reaction milling for scalable synthesis of N, P-codoped covalent organic polymers for metal-free bifunctional electrocatalysts
Sun et al. Iridium-doped ZIFs-derived porous carbon-coated IrCo alloy as competent bifunctional catalyst for overall water splitting in acid medium
Jia et al. Co2Ni alloy/N-doped CNTs composite as efficient hydrogen evolution reaction catalyst in alkaline medium
Zeng et al. Single-crystalline CoFe nanoparticles encapsulated in N-doped carbon nanotubes as a bifunctional catalyst for water splitting
Li et al. Facile synthesis of N, S co-doped porous carbons from a dual-ligand metal organic framework for high performance oxygen reduction reaction catalysts
Xu et al. A sheet-like MOF-derived phosphorus-doped porous carbons for supercapacitor electrode materials
He et al. Development of g-C3N4 activated hollow carbon spheres with good performance for oxygen reduction and selective capture of acid gases
Zhai et al. Porous layered cobalt nanocrystal/nitrogen-doped carbon composites as efficient and CO-resistant electrocatalysts for methanol oxidation reaction
Arunkumar et al. Impact of an incompatible atomic nickel-incorporated metal–organic framework on phase evolution and electrocatalytic activity of Ni-doped cobalt phosphide for the hydrogen evolution reaction
Ghanashyam et al. Flower-like molybdenum disulfide for efficient hydrogen and oxygen evolution reaction
Habibi et al. Synthesis of ternary CoZnAl layered double hydroxide and Co-embedded N-doped carbon nanotube hollow polyhedron nanocomposite as a bifunctional material for ORR electrocatalyst and supercapacitor electrode
Hai et al. Iron coordination polymer, Fe (oxalate)(H2O) 2 nanorods grown on nickel foam via one-step electrodeposition as an efficient electrocatalyst for oxygen evolution reaction

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17881269

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17881269

Country of ref document: EP

Kind code of ref document: A1