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Results for “mesoporous carbon”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Production of C 2 /C 3 Oxygenates from Planar Copper Nitride-Derived Mesoporous Copper via Electrochemical Reduction of CO 2

Electrochemical reduction of CO 2 provides an opportunity to produce fuels and chemicals in a carbon-neutral manner, assuming that CO 2 can be captured from the atmosphere. To do so requires efficient, selective, and stable catalysts. In this study, we report a highly mesoporous metallic Cu catalyst prepared by electrochemical reduction of thermally nitrided Cu foil. Under aqueous saturated CO 2 reduction conditions, the Cu 3 N-derived Cu electrocatalyst produces virtually no CH 4 , very little CO, and exhibits a faradaic efficiency of 68% in C 2+ products (C 2 H 4 , C 2 H 5 OH, and C 3 H 7 OH) at a current density of ~18.5 mA cm –2 and a cathode potential of -1.0 V versus the reversible hydrogen electrode. Under these conditions, the catalyst produces more oxygenated products than hydrocarbons. We show that surface roughness is a good descriptor of catalytic performance. The roughest surface reached 98% CO utilization efficiency for C 2+ product formation from CO 2 reduction and the ratio of oxygenated to hydrocarbon products correlates with the degree of surface roughness. These effects of surface roughness are attributed to the high population of undercoordinated sites as well as a high pH environment within the mesopores and adjacent to the surface of the catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Optimizing Vertical Crystallization for Efficient Perovskite Solar Cells by Buried Composite Layers

Planar-heterojunction perovskite solar cells (PSCs) have experienced rapid evolution in recent years because of the low-temperature processing, suitable alignment, and high mobility of the tin oxide buried contact layer. However, improper SnO 2 surface states and poor crystallinity of the top perovskite films are still the main obstacles for the planar PSCs in which performance always lags behind their mesoporous counterparts. Herein, a new buried contact is reported by introducing graphitic carbon nitride (g-C 3 N 4 ) into the commonly used SnO 2 which performs outstanding transmittance, conductivity, and surface states for a high-quality electron-transporting layer. Moreover, the vertical composition and crystallinity of the top perovskite film are manipulated by rich amino groups on the edge of the g-C 3 N 4 nanosheets which induce the prenucleation of the lead-rich species at the buried interface. Benefiting from the high-quality buried contacts and the optimized perovskite layers, the resultant PSCs achieve a champion efficiency of 21.5% with all photovoltaic parameters enhanced in comparison with their control counterparts (<20%).

planar-heterojunction perovskite solar cells↗
DOE OSTI2022

The effect of silica oxide support on the catalytic activity of nickel-molybdenum bimetallic catalyst toward ethanol steam reforming for hydrogen production

This work investigates the effects of molybdenum promoter and silica oxide (SiO 2 ) support morphology on the ethanol steam reforming (ESR) performance of Nickel-Molybdenum (NiMo) bimetallic catalysts. Ordered mesoporous SiO 2 (SBA-15) and commercial SiO 2 supports were used as the oxide support materials. The synthesized catalysts were prepared via the wet impregnation method and characterized via XRD, H 2 -TPR, BET, FTIR, and Raman techniques. This study shows that NiMo bimetallic catalyst supported on SBA-15 has superior catalytic activity and better coking resistance at an intermediate temperature of 600 ⁰C than commercial SiO 2 supported catalysts. The presence of a uniform mesoporous structure of SBA-15 with an average pore diameter of ~ 2 nm can obstruct the carbon formation, leading to improved coking resistance. The catalytic enhancement of NiMo bimetallic catalysts toward ESR can also be linked to the ability of Mo promoter in enhancing the interaction between NiMo nanoparticles and SiO 2 support materials and restraining agglomeration of Ni nanoparticles, which results in further improvement of NiMo nanoparticle dispersion and inhibit its sintering. The NiMo bimetallic catalysts supported on SBA-15 illustrated the high H 2 yield of ~ 54% and carbon conversion of ~ 89% with the excellent stability for ESR performed at 600 ⁰C and the steam-to-carbon ratio of 2 over 65 hours.

25 ENERGY STORAGE↗
DOE OSTI2025

Development of mesopores in superfine grain graphite neutron-irradiated at high fluence

Microstructural changes induced by neutron irradiation of superfine grain graphite G347A (Tokai Carbon, Japan) were examined by nitrogen adsorption at 77K and by three microscopy techniques (SEM, TEM and FIB-SEM tomography). The specimens were irradiated at doses of up to 30 dpa, covering stages before and after the turnaround fluence at three temperatures (300, 450, 750 °C) of their irradiation envelope. The initial graphite densification at low fluences did not produce any detectable effect in the pore size range (<350 nm) measured by gas adsorption. However, graphite irradiated at high fluences, after turnaround, showed severe structural changes. At all three temperatures and high irradiation fluences, gas adsorption revealed significant increase of the volume of narrow mesopores (<5–20nm) and up to five times increase of BET surface area, both in linear relationship with the relative volume expansion. Analysis of microscopy images showed multiplication of fine macropores (>50 nm) at high irradiation fluences and more structural changes on multiple scales, from nanometers to microns. This work demonstrates the unique ability of gas adsorption techniques to analyze open pores with sizes between sub-nanometer and sub-micron in bulk nuclear graphite, with supporting microscopy results.

I. Contescu, Cristian↗
DOE OSTI2022

Electrochemical characterization of evolving ionomer/electrocatalyst interactions throughout accelerated stress tests

Here, the degradation of polymer electrolyte membrane fuel cells (PEMFCs) catalyst layers used for heavy-duty vehicles was examined using a catalyst-specific accelerated stress test (AST). High surface area carbon supported dispersed Pt (Pt/HSC), annealed Pt (a-Pt/HSC) and PtCo (PtCo/HSC) alloy catalysts were examined over the course of 90,000 cycles by measuring changes in mass activity, O 2 transport resistance, electrochemical active surface area (ECSA), catalyst accessibility and ionomer-electrocatalyst interactions. Compared to a-Pt/HSC and Pt/HSC catalyst, the PtCo/HSC showed better initial mass activity, a larger initial mass transport loss, and faster degradation after the first 30k AST cycles, as a large portion of Co leached out during potential cycling. Pt/HSC showed higher initial performance relative to a-Pt/HSC but had faster degradation. STEM characterizations show that the ECSA losses are largely related to Pt dissolution resulting in either catalyst particle growth via the Ostwald ripening mechanism or redeposition in the membrane. Catalyst accessibility measurements showed decreased RH sensitivity for all three samples, while CO impedance measurements revealed a decrease in both Pt-water and carbon-water interactions. This implies that, Pt is either preferentially redepositing on the exterior of the carbon support, or that the ionomer is undergoing morphological changes enabling the enhanced intrusion of mesopores.

25 ENERGY STORAGE↗
DOE OSTI2021

Enhanced Performance of Pt Nanoparticles on Ni-N Co-Doped Graphitized Carbon for Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

Since the reaction rate and cost for cathodic catalyst in polymer electrolyte membrane fuel cells are obstacles for commercialization, the high-performance catalyst for oxygen reduction reaction is necessary. The Ni encapsulated with N-doped graphitic carbon (Ni@NGC) prepared with ethylenediamine and carbon black is employed as an efficient support for the oxygen reduction reaction. Characterizations show that the Ni@NGC has a large surface area and mesoporous structure that is suitable to the support for the Pt catalyst. The catalyst structure is identified and the size of Pt nanoparticles distributed in the narrow range of 2–3 nm. Four different nitrogen species are doped properly into graphitic carbon structure. The Pt/Ni@NGC shows higher performance than the commercial Pt/C catalyst in an acidic electrolyte. The mass activity of the Pt/Ni@NGC in fuel cell tests exhibits over 1.5 times higher than that of commercial Pt/C catalyst. The Pt/Ni@NGC catalyst at low Pt loading exhibits 47% higher maximum power density than the Pt/C catalyst under H2-air atmosphere. These results indicate that the Ni@NGC as a support is significantly beneficial to improving activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effect of Extended Aging and Oxidation on Linear Poly(propylenimine)-Mesoporous Silica Composites for CO 2 Capture from Simulated Air and Flue Gas Streams

Physical aging or degradation of amine-containing polymers and supported amine adsorbents is a critical issue that could limit practical application of such materials for CO 2 capture. However, to date, there is a scarcity of studies that evaluate the long-term stability of amine-based sorbents without the exclusive use of accelerated aging tests. Here, we demonstrate that extended aging (~2 years) of linear poly(propylenimine) (LPPI) confined in mesoporous silica (SBA-15) supports does not drastically impact the CO 2 adsorption performance under simulated flue gas (10% CO 2 ) and direct air capture (DAC, 400 ppm CO 2 ) conditions, although the behavior of the aged sorbents and polymers in the two CO 2 concentration regimes differs. Sorbents made with aged LPPI had modestly decreased CO 2 uptake performance (<~20% lower) compared to the fresh polymers, with overall good CO 2 cycling performance. The data indicate that only slow degradation occurs under the deployed ambient storage conditions. Even after extended aging, the LPPI-based sorbents preserved their ability to display stable temperature-swing cycling performance. In parallel, the impact of blending LPPI polymers of different number-average molecular weights, M n , is evaluated, seeking to understand its impact on adsorbent performance. We find that the results demonstrate that blends of two M n aged LPPI give similar CO 2 adsorption performance to adsorbents made from a single M n LPPI, suggesting that molecular weight will not negatively impact adsorbent performance in the studied M n range. After an accelerated oxidation experiment, the aged LPPI sorbents retained a larger portion of the samples’ original performance when cycling under simulated flue gas conditions than under DAC conditions. However, in each case, the oxidized sorbents could be cycled repeatedly with consistent uptake performance. Overall, these first of their kind extended aging tests suggest that LPPI-based amine adsorbents offer promise for long term, stable use in carbon capture applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Graphene oxide precursor effects on 3D-printed carbon scaffolds

Manganese oxide (MnO 2 ), an earth-abundant material, is a promising component for energy storage devices, with uses in both pseudocapacitors and batteries. However, high MnO 2 loading often leads to reduced performance due to poor ion diffusion. 3D printing, particularly using the direct ink writing (DIW) technique, offers a solution by enabling the fabrication of electrodes with hierarchical porous structures and open channels that enhance mass transport and ion diffusion. Previous work demonstrated that 3D-printed graphene aerogels with MnO 2 coatings exhibited excellent electrochemical performance, even with thick electrodes, due to their optimized structure. Building on this work, the current study investigates the performance differences between aerogels developed using graphene oxide (GO) and reduced graphene oxide (rGO) as carbon precursors. Both materials were incorporated into thixotropic inks, 3D-printed into lattice structures, and carbonized. Despite expected similarities between the final graphene aerogel, rGO-based aerogels exhibited superior areal capacitance, compared to GO-based aerogels. These differences are attributed to the lower oxygen content and defect density of rGO, which influence its interaction with cellulose viscosifiers in the ink formulation. Brunauer–Emmett–Teller (BET) surface area analysis revealed that rGO aerogels exhibit a larger surface area and mesoporous structure, further enhancing their performance. When coated with MnO 2 , rGO-based aerogels maintained their superior capacitive behavior over GO-based aerogels. This study highlights the effect of carbon precursor on the end performance of graphene aerogels.

Materials science↗
DOE OSTI2023

Micro‐ and Nanoscale Heterogeneities in Zeolite Beta as Measured by Atom Probe Tomography and Confocal Fluorescence Microscopy

Micro- and nanoscale information on the activating and deactivating coking behaviour of zeolite catalyst materials increases our current understanding of many industrially applied processes, such as the methanol-to-hydrocarbon (MTH) reaction. Atom probe tomography (APT) was used to reveal the link between framework and coke elemental distributions in 3D with sub-nanometre resolution. APT revealed 10–20 nanometre-sized Al-rich regions and short-range ordering (within nanometres) between Al atoms. With confocal fluorescence microscopy, it was found that the morphology of the zeolite crystal as well as the secondary mesoporous structures have a great effect on the microscale coke distribution throughout individual zeolite crystals over time. Additionally, a nanoscale heterogeneous distribution of carbon as residue from the MTH reaction was determined with carbon-rich areas of tens of nanometres within the zeolite crystals. Finally, a short length-scale affinity between C and Al atoms, as revealed by APT, indicates the formation of carbon-containing molecules next to the acidic sites in the zeolite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Chemistry and Dynamics of Supercritical Carbon Dioxide and Methane in the Slit Pores of Layered Silicates

In the mid 2010s, high-pressure diffraction and spectroscopic tools opened a window into the molecular-scale behavior of fluids at the conditions of many CO 2 sequestration and shale/tight gas reservoirs - conditions where CO 2 and CH 4 are present as variably wet supercritical fluids. Integrating high-pressure spectroscopy and diffraction with molecular modeling has revealed much about the ways that supercritical CO 2 and CH 4 behave in reservoir components, particularly in the slit-shaped micro- and meso-pores of layered silicates (phyllosilicates) abundant in caprocks and shales. This Account summarizes how supercritical CO 2 and CH 4 behave in the slit pores of swelling phyllosilicates as functions of the H 2 O activity, framework structural features, and charge-balancing cation properties at 90 bar and 323 K – conditions similar to a reservoir at ~1 km depth. Slit pores containing cations with large radii, low hydration energy, and large polarizability readily interact with CO 2 , allowing CO 2 and H 2 O to adsorb and co-exist in these interlayer pores over a wide range of fluid humidities. In contrast, cations with small radii, high hydration energy, and low polarizability weakly interact with CO 2 leading to reduced CO 2 uptake and a tendency to exclude CO 2 from interlayers when H 2 O is abundant. The reorientation dynamics of confined CO 2 depends on the interlayer pore height, which is strongly influenced by the cation properties, framework properties, and fluid humidity. The silicate structural framework also influences CO 2 uptake and behavior - for example, smectites with increasing F-for-OH substitution in the framework take up greater quantities of CO 2 . Reactions that trap CO 2 in carbonate phases have been observed in thin H 2 O films near smectite surfaces, including a dissolution-reprecipitation mechanism when the edge surface area is high and an ion exchange-precipitation mechanism when the interlayer cation can form a highly insoluble carbonate. In contrast, supercritical CH 4 does not readily associate with cations, does not react with smectites, and is only incorporated into interlayer slit mesopores when (i) the pore has a $z$-dimension large enough to accommodate CH 4 , (ii) the smectite has low charge and (iii) the H 2 O activity is low. In conclusion, the adsorption and displacement of CH 4 by CO 2 and vice-versa have been studied on the molecular scale in one shale, but opportunities remain to examine behavioral details in this more complicated, slit-pore inclusive system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Breaking the Energy Barrier of Heavy Metal Ion Diffusion in Micropores with Mesoporous 3D Graphene for Fast and Efficient Cu2+ Removal

Efficient removal of heavy metals from water critically depends not only on adsorption capacity but also on ion diffusion kinetics and the associated energy barriers. In conventional carbon adsorbents, severe diffusion confinement within micropores restricts ion transport, resulting in sluggish adsorption kinetics and large apparent activation energies despite high specific surface areas. Here, we demonstrate that this fundamental limitation is overcome by engineering meso/macroporous architectures in the 3D graphene materials synthesized via our discovered alkali-metal reactions with\\\\r\\\\n2\\\\r\\\\nCO. The unique 3D graphene materials possess defect-rich graphene frameworks with interconnected meso/macroporous networks, exhibiting simultaneously high surface area and greatly enhanced meso/macropore volume that enable efficient access to adsorption sites. As a result, the Cu2+ adsorption on 3D graphene proceeds with very low activation energies (4.98 kJ mol–1), which is almost 4 times smaller than on activated carbon (23.1 kJ mol–1). This finding offers a promising platform for efficient and sustainable water purification.

25 ENERGY STORAGE↗
DOE OSTI2020

Revealing Molecular Mechanisms in Hierarchical Nanoporous Carbon via Nuclear Magnetic Resonance

Hierarchical nanoporous carbons (HNC) have been proven to be an effective adsorbent for the adsorption of volatile organic compounds (VOCs) and CO 2 . However, questions remain regarding the hierarchical structure regulation, the adsorption mechanisms of adsorbate uptake, and interactions within the HNC. Here, we synthesize HNC from wood, using a microwave-induced heating method incorporating K 2 CO 3 activation. Our HNC exhibit Murray's law multiscale structures, prompting a molecular-scale study of adsorbate adsorption via nuclear magnetic resonance (NMR). NMR chemical shifts are consistent with ring-current effects from the adsorbent. Our NMR technique provides a convenient way to quantitate adsorption of adsorbate in HNC. VOC vapor adsorption results show NMR chemical-shift changes with time, suggesting initial adsorption into mesopores, followed by diffusion into micropores. Schroeder's paradox is demonstrated by differences in observed shifts for adsorbed liquid vis-à-vis vapor phase in these HNC. These HNC show high CO 2 adsorption capacity, portending applications to carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Designing hierarchical nanoporous membranes for highly efficient gas adsorption and storage

Nanoporous membranes with two-dimensional materials such as graphene oxide have attracted attention in volatile organic compounds (VOCs) and H 2 adsorption because of their unique molecular sieving properties and operational simplicity. However, agglomeration of graphene sheets and low efficiency remain challenging. Therefore, we designed hierarchical nanoporous membranes (HNMs), a class of nanocomposites combined with a carbon sphere and graphene oxide. Hierarchical carbon spheres, prepared following Murray’s law using chemical activation incorporating microwave heating, act as spacers and adsorbents. Hierarchical carbon spheres preclude the agglomeration of graphene oxide, while graphene oxide sheets physically disperse, ensuring structural stability. The obtained HNMs contain micropores that are dominated by a combination of ultramicropores and mesopores, resulting in high VOCs/H 2 adsorption capacity, up to 235 and 352 mg/g at 200 ppmv and 3.3 weight % (77 K and 1.2 bar), respectively. Our work substantially expands the potential for HNMs applications in the environmental and energy fields.

42 ENGINEERING↗
DOE OSTI2020

Mesoporous silica-encapsulated gold core–shell nanoparticles for active solvent-free benzyl alcohol oxidation

Silica-encapsulated gold core@shell nanoparticles (Au@SiO2 CSNPs) were synthesized via a bottom-up procedure and used to catalyze the selective oxidation of benzyl alcohol. The pore size, morphology, crystallinity and composition of Au@SiO2 was evaluated using non-local density functional theory, transmission electron microscopy, high-energy x-ray diffraction and inductively coupled plasma-mass spectroscopy, respectively. The nanoparticles exhibit a mesoporous shell with an average thickness of 25.5 Å which can enhance selectivity via preferential transport of the desired product (i.e., benzaldehyde) relative to larger, undesired products (i.e, benzoic acid/benzyl benzoate). GC-FID analysis revealed the addition of potassium carbonate to the solvent-free oxidation of benzyl alcohol increased conversion from 17.3 to 60.4% while decreasing selectivity from 98.7 to 75.0%. Under equivalent conditions, a bare gold nanoparticle control catalyst deposited on a silica support with a similar gold surface area took 6 times as long to reach the same conversion, achieving only 49.4% selectivity. These results suggest that the pore size distribution within the inert silica shell of Au@SiO2 CSNPs inhibits the formation of undesired products to facilitate the selective oxidation of benzaldehyde despite a basic environment, which reduces selectivity under typical conditions. The CSNPs demonstrated a much lower activation energy than the Au-SiO2 control catalyst, 37 ± 1.9 kJ/mol and 72 ± 7.1 kJ/mol, respectively. Thiele modulus analysis indicates the CSNP pore structure does not create a mass transport limitation due to the nano-scale path of diffusion through the pore structure to the active surface. The lower activation energy and mesopore distribution together suggest the Au@SiO2 catalyst demonstrates higher activity through beneficial in-pore orientation, both reducing competitive adsorption and promoting a single, lower activation energy mechanistic pathway.

benzyl alcohol oxidation, catalysis, confinement↗
DOE OSTI2020

Synthesis of Interface-Driven Tunable Bandgap Metal Oxides

Mixed bandgap and bandgap tunability in semiconductors is critical in expanding their use. Composition altera-tions through single-crystal epitaxial growth and formation of multi-layer tandem structures are often employed to achieve mixed bandgaps albeit with limited tunability. In this study, self-assembled one-dimensional coordination polymers provide a fac-ile synthon and template for graphitic C-doped mesoporous oxides, gC-β-Ga 2 O 3 or gC-In 2 O 3 via controlled oxidative ligand ablation. These materials have mixed bandgaps, and colors, depending on amount of gC present. The carbon-oxide interface leads to induced gap states, hence, a stoichiometrically tunable band structure. Structurally, a multi-scale porous network percolating throughout the material is realized. The nature of heat-treatment and top-down process allows for facile tunabil-ity and formation of mixed bandgap metal oxides through controlled carbon deposition. As a proof of concept, gC-β-Ga 2 O 3 was utilized as a photocatalyst for CO 2 reduction, which demonstrated excellent selectivity and conversion rates into CH 4 and CO.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis

Heptazine-based conjugated polymeric carbon nitrides (PCNs) are promising metal-free photocatalysts, yet their synthesis is challenging due to the electron-deficiency and insolubility of heptazine units. Indeed, heptazine-containing polymers have only been prepared through nucleophilic substitution with amines by using toxic cyameluric chloride as the starting material. Herein, we report the novel and environmentally friendly method for preparing heptazine-based mesoporous PCNs with hydrazone links formed through a simple Schiff base condensation of melem-NH 2 and aldehydes. Unlike cyameluric chloride, melem-NH 2 is non-toxic, stable, and can be readily obtained from melem and hydrazine in solution. We demonstrate that the hydrazone linkages and the heptazine units synergistically enhance the photocatalytic activity of PCNs in visible-light-driven aerobic oxidation of benzyl alcohol to benzaldehyde. In particular, the polymer constructed from melem-NH2 and p-phthalaldehyde shows 17 times more activity than graphitic carbon nitride (g-C 3 N 4 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Ru Single Atoms on One-Dimensional CF@g-C 3 N 4 Hierarchy as Highly Stable Catalysts for Aqueous Levulinic Acid Hydrogenation

Herein, we report a stable catalyst with Ru single atoms anchored on a one-dimensional carbon fiber@graphitic carbon nitride hierarchy, by assembling wet wipes composed of fiber-derived carbon fiber (CF), melamine-derived graphitic carbon nitride (g-C3N4) and RuCl3 before NaBH4 reduction. The atomically dispersed Ru species (3.0 wt%) are tightly attached via N-coordination provided by exterior g-C3N4 nanosheets, and further stabilized by the interior mesoporous CF. The obtained CF@g-C3N4–Ru SAs catalyst can be cycled six times without notable leaching of Ru or loss of GVL yield in the acidic media. This catalyst is more stable than Ru nanoparticles supported on CF@g-C3N4, as well as Ru single atoms anchored on CF and g-C3N4, and proves to be one of the most efficient metal catalysts for aqueous LA hydrogenation to γ-valerolactone (GVL). The isolated Ru atoms by strong N-coordination, and their enhanced electron/mass transfer afforded by the one-dimensional hierarchy, can be responsible for the excellent durability of CF@g-C3N4–Ru SAs under harsh reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗