Zhe Qiang

A nitrogen doped carbonized metal–organic framework for high stability room temperature sodium–sulfur batteries

A nanoporous nitrogen doped carbon matrix was prepared by carbonization of metal–organic framework zeolitic imidazolate framework (ZIF-8) precursors. The doped carbon matrix was melt-infiltrated with sulfur to form a carbonized ZIF-8/S composite. The composite material exhibited good performance as the cathode for room-temperature sodium–sulfur battery (Na–S) systems. A reversible specific capacity of around 1000 mA h g−1 could be achieved at a rate of 0.1C; and a reversible specific capacity of 500 mA h g−1 was obtained at a rate of 0.2C after 250 cycles. The good performance of the Na–S battery could be attributed to the synergistic effect from the nanoporosity of the carbon matrix and the high nitrogen-doping content (ca. ∼18 at%). These attributes enhanced the entrapment of the sulfur molecules inside the carbon matrices.

Large-Scale Roll-to-Roll Fabrication of Ordered Mesoporous Materials using Resol-Assisted Cooperative Assembly

Roll-to-roll (R2R) processing enables the rapid fabrication of large-area sheets of cooperatively assembled materials for production of mesoporous materials. Evaporation induced self-assembly of a nonionic surfactant (Pluronic F127) with sol-gel precursors and phenolic resin oligomers (resol) produce highly ordered mesostructures for a variety of chemistries including silica, titania, and tin oxide. The cast thick (>200 μm) film can be easily delaminated from the carrier substrate (polyethylene terephthalate, PET) after cross-linking the resol to produce meter-long self-assembled sheets. The surface areas of these mesoporous materials range from 240 m(2)/g to >1650 m(2)/g with these areas for each material comparing favorably with prior reports in the literature. These R2R methods provide a facile route to the scalable production of kilograms of a wide variety of ordered mesoporous materials that have shown potential for a wide variety of applications with small-batch syntheses.

Unidirectional self-assembly of soft templated mesoporous carbons by zone annealing

Surfactant or block copolymer-templated mesoporous films have been extensively explored, but achieving mesostructure coherence and unidirectional orientation over macroscopic dimensions has remained quite challenging for these self-assembled systems. Here, we extend the concepts associated with zone refinement of crystalline materials to soft templated mesoporous carbon films based on the cooperative assembly of commercial non-ionic surfactants (block copolymers) and phenolic resin oligomers (resol) to provide macroscopic alignment of both cubic (FDU-16) and hexagonal (FDU-15) mesostructures. The average orientation of these mesophases is determined from rotation grazing incidence small angle X-ray scattering (GISAXS) measurements. For FDU-15 templated by Pluronic P123, the orientation factor for the zone-annealed film is 0.98 based on the average of the second Legendre polynomial, but this orientation deteriorates significantly during carbonization. Notably, a thermal stabilization step following zone annealing preserves the orientation of the mesostructure during carbonization. The orientation factor for an isotropic cubic structure (FDU-16 templated by Pluronic F127) is only 0.48 (based on the 111 reflection with incident angle 0.15°) for the same zone annealing protocol, but this illustrates the versatility of zone annealing to different mesostructures. Unexpectedly, zone annealing of FDU-15 templated by Pluronic F127 leads to stabilization of the mesostructure through carbonization, whereas this structure collapses fully during carbonization even after extended oven annealing; despite no clear macroscopic orientation of the cylindrical mesostructure from zone annealing. Thermal zone annealing provides a simple methodology to produce highly ordered and macroscopically oriented stable mesoporous carbon films, but the efficacy is strongly tied to the mobility of the template during the zone annealing.

Morphology Control in Mesoporous Carbon Films Using Solvent Vapor Annealing

Ordered mesoporous (2-50 nm) carbon films were fabricated using cooperative self-assembly of a phenolic resin oligomer with a novel block copolymer template (poly(styrene-block-N,N-dimethyl-n-octadecylamine p-styrenesulfonate), (PS-b-PSS-DMODA)) synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Due to the high Tg of the PS segment and the strong interactions between the phenolic resin and the PSS-DMODA, the segmental rearrangement is kinetically hindered relative to the cross-linking rate of the phenolic resin, which inhibits long-range ordering and yields a poorly ordered mesoporous carbon with a broad pore size distribution. However, relatively short exposure (2 h) to controlled vapor pressures of methyl ethyl ketone (MEK) yields significant improvements in the long-range ordering and narrows the pore size distribution. The average pore size increases as the solvent vapor pressure during annealing increases, but an upper limit of p/p0 = 0.85 exists above which the films dewet rapidly during solvent vapor annealing. This approach can be extended using mesityl oxide, which has similar solvent qualities to MEK, but is not easily removed by ambient air drying after solvent annealing. This residual solvent can impact the morphology that develops during cross-linking of the films. These results illustrate the ability to fine-tune the mesostructure of ordered mesoporous carbon films through simple changes in the processing without any compositional changes in the initial cast film.

A binary metal organic framework derived hierarchical hollow Ni3S2/Co9S8/N-doped carbon composite with superior sodium storage performance

A binary Ni/Co metal organic framework (Ni–Co-MOF) with a hollow-sphere structure that is decorated with cone-shaped protrusions was prepared via a facile solvothermal reaction. Carbonization and sulfurization of the Ni–Co-MOF produced a Ni3S2/Co9S8/N-doped carbon composite that retained the hierarchical structure. The final composite material presents exceptional electrochemical performance when used as an anode in sodium-ion batteries. A reversible specific capacity of 419.9 mA h g−1 at a current density of 0.1 A g−1 was achieved after 100 cycles, with an exceptional capacity retention of 98.6%. Furthermore, superior rate capability was also demonstrated: an average capacity of 323.2 mA h g−1 at a current density of 2 A g−1 can be achieved. This exceptional performance can be attributed to the unique nano-architecture derived from the MOF precursor, as the resultant material possesses an ideal profile for an excellent anode material: ultrafine Ni3S2 and Co9S8 particles (∼7 nm), a hollow, porous structure, and an ultrathin N-doped carbon coating.

Facile control of long range orientation in mesoporous carbon films with thermal zone annealing velocity

Ordered mesoporous carbons exhibit appealing properties for many applications, but their function and performance can depend critically on their structure. The in-plane orientation of 2D cylinders from the cooperative assembly of Pluronic P123 and resol has been controlled by application of cold zone annealing (CZA). By varying the moving rate, the preferential in-plane orientation of the self-assembled cylinders can be tuned through the entire 180° range possible from ϕ = 50° to ϕ = -130° (relative to the moving direction). At a moving rate of 2 μm s(-1), this simple and easy CZA process leads to cylinders that are well aligned parallel to the moving direction with a high orientational factor of S = 0.98. Moreover, the in-plane oriented cylinders can be nearly perfectly aligned transverse to the moving direction (S = 0.95) by simply decreasing the moving velocity to 0.5 μm s(-1). We attribute the parallel alignment to the flow that develops from the motion of the thermal gradients, while the transverse alignment is related to flow cessation (inertial effect). The preferential orientation is retained through the carbonization process, but there is some degradation in orientation due to insufficient crosslinking of the resol during CZA; this effect is most prominent for the higher moving rates (less time for crosslinking), but can be overcome by post-CZA annealing at uniform elevated temperatures to further crosslink the resol. CZA is a simple and powerful method for fabricating well-aligned and self-assembled mesoporous carbon films over large areas.

Control of Ordering and Structure in Soft Templated Mesoporous Carbon Films by Use of Selective Solvent Additives

The structure of ordered mesoporous carbons fabricated using poly(styrene-block-N,N,-dimethyl-n-octadecylamine p-styrenesulfonate) (PS-b-PSS-DMODA) as the template and phenolic resin (resol) as the carbon source can be easily manipulated by inclusion of low concentrations of low volatility selective solvents in the casting solution. Casting from neat methyl ethyl ketone yields a disordered structure even upon thermal annealing. However, addition of both dioctyl phthalate (DOP, PS selective) and dimethyl sulfoxide (DMSO, resol and PSS-DMODA selective) at modest concentrations to this casting solution provides sufficient mobility to produce highly ordered films with cylindrical mesopores. The DOP acts to swell the hydrophobic domain and can more than double the mesopore size, while the DMSO acts to swell the resol phase. Moreover, the surface area of the mesoporous carbons increases significantly as the meosopore size increases. This is a result of the decrease in wall thickness, which can be ascertained by the constant d-spacing of the mesostructure as the pore size increases. This behavior is counter to the typical effect of pore swelling agents that increase the pore size and decrease the surface area. Moreover, with only 4 wt % DOP/DMSO in the solution (20 wt % relative to solids), the scattering profiles exhibit many orders of diffraction, even upon carbonization, which is not typically observed for soft templated films. Variation in the concentration of DOP and DMSO during casting enables facile tuning of the structure of mesoporous carbon films.

Role of Amphiphilic Block Copolymer Composition on Pore Characteristics of Micelle-Templated Mesoporous Cobalt Oxide Films

Block copolymer templating is a versatile approach for the generation of well-defined porosity in a wide variety of framework chemistries. Here, we systematically investigate how the composition of a poly(methoxy poly[ethylene glycol] methacrylate)-block-poly(butyl acrylate) (PMPEG-PBA) template impacts the pore characteristics of mesoporous cobalt oxide films. Three templates with a constant PMPEG segment length and different hydrophilic block volume fractions of 17%, 51%, and 68% for the PMPEG-PBA are cooperatively assembled with cobalt nitrate hexahydrate and citric acid. Irrespective of template composition, a spherical nanostructure is templated and elliptical mesostructures are obtained on calcination due to uniaxial contraction of the film. The average pore size increases from 11.4 ± 2.8 to 48.5 ± 4.3 nm as the length of the PBA segment increases as determined from AFM. For all three templates examined, a maximum in porosity (∼35% in all cases) and surface area is obtained when the precursor solids contain 35-45 wt % PMPEG-PBA. This invariance suggests that the total polymer content drives the structure through interfacial assembly. The composition for maximizing porosity and surface area with the micelle-templating approach results from a general decrease in porosity with increasing cobalt nitrate hexahydrate content and the increasing mechanical integrity of the framework to resist collapse during template removal/crystallization as the cobalt nitrate hexahydrate content increases. Unlike typical evaporation induced self-assembly with sol-gel chemistry, the hydrophilic/hydrophobic composition of the block copolymer template is not a critical component to the mesostructure developed with micelle-templating using metal nitrate-citric acid as the precursor.

Relationship between crosslinking and ordering kinetics for the fabrication of soft templated (FDU-16) mesoporous carbon thin films

Although the fabrication of mesoporous carbon films through the cooperative assembly of phenolic resin oligomers (resol) and block copolymers is well-established, these methods generally rely upon simply following protocols developed for analogous bulk powders despite growing evidence of significant differences between thin films and bulk powders. Here, we examine the chemical evolution of resol through spectroscopically tracking the methylol content for films with and without a common templating agent (Pluronic F127). At lower temperature (100 °C and 120 °C), the crosslinking rate is not impacted by the presence of the template, while the addition of the Pluronic template decreases the reaction rate at higher temperatures (140 °C and 160 °C). At all conditions examined, the crosslinking kinetics of resol can be fit using the Jander model. in situ grazing incidence small angle X-ray scattering illustrates that the mesostructural evolution is not highly correlated with the chemical changes during crosslinking. With this knowledge, a shortened processing schedule (3 h total) was devised in place of the standard 24 h thermopolymerization without adversely impacting the ordered structure of the mesoporous film and this protocol significantly increases (almost double) the porosity of the film.

Nanoporous Nonwoven Fibril-Like Morphology by Cooperative Self-Assembly of Poly(ethylene oxide)-block-Poly(ethyl acrylate)-block-Polystyrene and Phenolic Resin

Cooperative self-assembly of block copolymers with (in)organic precursors effectively generates ordered nanoporous films, but the porosity is typically limited by the need for a continuous (in)organic phase. Here, a network of homogeneous fibrous nanostructures (≈20 nm diameter cylinders) having high porosity (≈ 60%) is fabricated by cooperative self-assembly of a phenolic resin oligomer (resol) with a novel, nonfrustrated, ABC amphiphilic triblock copolymer template, poly(ethylene oxide)-block-poly(ethyl acrylate)-block-polystyrene (PEO-b-PEA-b-PS), via a thermally induced self-assembly process. Due to the high glass transition temperature (Tg) of the PS segments, the self-assembly behavior is kinetically hindered as a result of competing effects associated with the ordering of the self-assembled system and the cross-linking of resol that suppresses segmental mobility. The balance in these competing processes reproducibly yields a disordered fibril network with a uniform fibril diameter. This nonequilibrium morphology is dependent on the PEO-b-PEA-b-PS to resol ratio with an evolution from a relatively open fibrous structure to an apparent poorly ordered mixed lamellae-cylinder morphology. Pyrolysis of these former films at elevated temperatures yields a highly porous carbon film with the fibril morphology preserved through the carbonization process. These results illustrate a simple method to fabricate thin films and coatings with a well-defined fiber network that could be promising materials for energy and separation applications.