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Verma, Gaurav

Publications and source records attributed to Verma, Gaurav.

15 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Bifunctional Metal‐Organic Nanoballs Featuring Lewis Acidic and Basic Sites as a New Platform for One‐Pot Tandem Catalysis

Abstract The design and synthesis of polyhedra using coordination‐driven self‐assembly has been an intriguing research area for synthetic chemists. Metal‐organic polyhedra are a class of intricate molecular architectures that have garnered significant attention in the literature due to their diverse structures and potential applications. Hereby, we reportCu‐MOP, a bifunctional metal‐organic cuboctahedra built using 2,6‐dimethylpyridine‐3,5‐dicarboxylic acid and copper acetate at room temperature. The presence of both Lewis basic pyridine groups and Lewis acidic copper sites imparts catalytic activity to Cu‐MOP for the tandem one‐pot deacetalization‐Knoevenagel/Henry reactions. The effect of solvent system and time duration on the yields of the reactions was studied, and the results illustrate the promising potential of these metal‐organic cuboctahedra, also known as nanoballs for applications in catalysis.

Chemistry↗
DOE OSTI2024

Tailoring the Coordination Micro‐Environment in Nanotraps for Efficient Platinum/Palladium Separation

Abstract Recovering platinum group metals from secondary resources is crucial to meet the growing demand for high‐tech applications. Various techniques are explored, and adsorption using porous materials has emerged as a promising technology due to its efficient performance and environmental beingness. However, the challenge lies in effectively recovering and separating individual platinum group metals (PGMs) given their similar chemical properties. Herein, a breakthrough approach is presented by sophisticatedly tailoring the coordination micro‐environment in a series of aminopyridine‐based porous organic polymers, which enables the creation of platinum‐specific nanotraps for efficient separation of binary PGMs (platinum/palladium). The newly synthesized POP‐o2NH 2 ‐Py demonstrates record uptakes and selectivity toward platinum over palladium, with the amino groups adjacent to the pyridine moieties being vital in improving platinum binding performance. Further breakthrough experiments underline its remarkable ability to separate platinum and palladium. Spectroscopic analysis reveals that POP‐o2NH 2 ‐Py offers a more favorable coordination fashion to platinum ions compared to palladium ions owing to the greater interaction between N and Pt 4+ and stronger intramolecular hydrogen bonding between the amino groups and four coordinating chlorines at platinum. These findings underscore the importance of fine‐tuning the coordination micro‐environment of nanotraps through subtle modifications that can greatly enhance the selectivity toward the desired metal ions.

Chemistry↗
DOE OSTI2024

Cross-Feature Transfer Learning for Efficient Tensor Program Generation

Tuning tensor program generation involves navigating a vast search space to find optimal program transformations and measurements for a program on the target hardware. The complexity of this process is further amplified by the exponential combinations of transformations, especially in heterogeneous environments. This research addresses these challenges by introducing a novel approach that learns the joint neural network and hardware features space, facilitating knowledge transfer to new, unseen target hardware. A comprehensive analysis is conducted on the existing state-of-the-art dataset, TenSet, including a thorough examination of test split strategies and the proposal of methodologies for dataset pruning. Leveraging an attention-inspired technique, we tailor the tuning of tensor programs to embed both neural network and hardware-specific features. Notably, our approach substantially reduces the dataset size by up to 53% compared to the baseline without compromising Pairwise Comparison Accuracy (PCA). Furthermore, our proposed methodology demonstrates competitive or improved mean inference times with only 25–40% of the baseline tuning time across various networks and target hardware. The attention-based tuner can effectively utilize schedules learned from previous hardware program measurements to optimize tensor program tuning on previously unseen hardware, achieving a top-5 accuracy exceeding 90%. This research introduces a significant advancement in autotuning tensor program generation, addressing the complexities associated with heterogeneous environments and showcasing promising results regarding efficiency and accuracy.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Methane storage in flexible and dynamical metal–organic frameworks

Recently, there has been significant interest in methane as an abundant and cleaner burning alternative to fossil fuels. Consequently, the design of media capable of the storage of methane under practical conditions has become an area of significant interest to the scientific community. While metal−organic frameworks have seen pronounced examination for this application, flexible metal−organic framework variants have been little examined despite having tremendous promise for methane storage applications. This work provides an overview of the current state of the art regarding the investigation of these systems for the purpose of providing a baseline for future research.

Forrest, Katherine A.↗
DOE OSTI2022

Self-Adjusting Metal–Organic Framework for Efficient Capture of Trace Xenon and Krypton

The capture of the xenon and krypton from nuclear reprocessing off-gas is essential to the treatment of radioactive waste. Although various porous materials have been employed to capture Xe and Kr, the development of high-performance adsorbents capable of trapping Xe/Kr at very low partial pressure as in the nuclear reprocessing off-gas conditions remains challenging. Herein, we report a self-adjusting metal-organic framework based on multiple weak binding interactions to capture trace Xe and Kr from the nuclear reprocessing off-gas. The self-adjusting behavior of ATC-Cu and its mechanism have been visualized by the in-situ single-crystal X-ray diffraction studies and theoretical calculations. The self-adjusting behavior endows ATC-Cu unprecedented uptake capacities of 2.65 and 0.52 mmol g -1 for Xe and Kr respectively at 0.1 bar and 298 K, as well as the record Xe capture capability from the nuclear reprocessing off-gas. Further, our work not only provides a benchmark Xe adsorbent but proposes a new route to construct smart materials for efficient separations.

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

Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors

Postsynthetic modification (PSM) in metal-organic frameworks (MOFs) can introduce multiple functionalities and alter the structural function for the desired application. However, the PSM of the coordination site faces the challenges of structural collapse or incompatibility between the original metal site and the newly formed coordination group. Herein, we developed a novel concept of introducing “primary” and “secondary” nodes, coexisting in a water-stable, Zr-based heterometallic MOF, [Zr6(µ3-OH)8(OH)8][CuI4(L1)4]2 (1-SH-a, H2L1 = 6-mercaptopyridine-3-carboxylic acid). The post-synthetic oxidation at the coordination site was successfully achieved in the “secondary” nodes [CuI4(L1)4]4-, while the robust “primary” nodes [Zr6(µ3-OH)8(OH)8]8+ stabilized the whole framework to form [Zr6(µ3-OH)8(OH)8][(CuI0.44CuII0.56(OH)0.56)4(L2)4]2 (1-SO3H, H2L2 = 6-sulfonicotinic acid). PSM of 1-SH-a to form 1-SO3H dramatically tuned the catalytic properties toward the styrene oxide ring-opening reaction to give a regioselectivity of primary alcohol (A) of ~99% compared with 1-SH-a (~71%).

Han, Yi↗
DOE OSTI2019

Pore environment engineering in metal–organic frameworks for efficient ethane/ethylene separation

Selective adsorption of trace amounts of C 2 H 6 from bulk C 2 H 4 is a significantly important and extremely challenging task in industry, which requires an adsorbent with specific pore properties. In this work, we describe a strategy for adjusting the pore environment of metal–organic frameworks (MOFs) by introducing different amounts of methyl groups in the channel to enhance the guest–host interaction between C 2 H 6 and the framework. To prove this concept, 2,3,5,6-tetramethylterephthalic acid (TMBDC) was deliberately added to a microporous MOF, Ni(BDC)(DABCO) 0.5 , affording a series of mixed-ligand materials, Ni(BDC) 1– x (TMBDC) x (DABCO) 0.5 ( x = 0, 0.2, 0.45, 0.71, 1), having different pore environments. Significantly, these mixed-ligand materials demonstrated improved performance in terms of the adsorption capacity of C 2 H 6 and C 2 H 4 with an unprecedented C 2 H 6 uptake of 2.21 mmol g –1 for Ni(TMBDC)(DABCO) 0.5 at 0.0625 bar and 298 K. With the best theoretical C 2 H 6 /C 2 H 4 selectivity predicted by IAST, Ni(TMBDC)(DABCO) 0.5 exhibited effective separation of C 2 H 6 /C 2 H 4 (1/15, v/v) and great recyclability in five consecutive adsorption/desorption cycles throughout the breakthrough experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Partially Interpenetrated NbO Topology Metal–Organic Framework Exhibiting Selective Gas Adsorption

We report on the first partially interpenetrated metal–organic framework (MOF) with NbO topology for its ability to separate methane from carbon dioxide and permanently sequester the greenhouse gas CO2. The MOF, Cu2(pbpta) (H4pbpta = 4,4',4'',4'''-(1,4-phenylenbis(pyridine-4,2-6-triyl))-tetrabenzoic acid), crystallizes in the monoclinic C2/m space group and has a 2537 m2/g Brunauer, Emmett and Teller surface area with an 1.06 cm3/g pore volume. The MOF exhibits selective adsorption of CO2 over CH4 as well as that of C2H6 and C2H4 over CH4. Cu2(pbpta) additionally shows excellent catalytic efficacy for the cycloaddition reaction of CO2 with epoxides to produce industrially important cyclic carbonates using solvent-free conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Carbon nanofibers suppress fungal inhibition of seed germination of maize (Zea mays) and barley (Hordeum vulgare L.) crop

Carbon nanofibers (CNFs) are one of allotropes of carbon, consists of graphene layers arrangement in the form of stacked cones or like a cup diameter in nanometer and several millimeters in length. Their extraordinary mechanical, chemical and electronic properties are due to their small size. CNFs have been successfully applied in field of medicine in variety of diagnostic methods. They proven to be an excellent system for drug delivery, tissue regeneration, biosensor etc. This research focuses the applications of CNFs in all fields of Agriculture. In the we treated some fungal disease seed of maize and barley using functionalised CNFs. We find that the tested seeds grow just as well as the healthy seeds whereas the untreated fungal disease seeds, by themselves show very poor germination and seedling growth. This simple experiment shows the extraordinary ability of Carbon nanofibers in carrying effectively inside the germinated seeds.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Interaction of Nano-Sized Materials With Polymer Chains in Polymer-Nanocomposite Thin Films-An AFM Perspective

Nanocomposite thin films were prepared with polyurethane as a matrix and organically modified clay as a filler. The interfacial interaction between the exfoliated clay nanoplatelets and the polymeric chains has been investigated by using Atomic Force Microscopy (AFM). The nanoclay platelets show a preferential association with the hard domains of polyurethane matrix on the surface of the thin films. The pendant hydroxyl group on the nanoplatelets attract the isocyanate of the polyisocyanate and a urethane group is formed. This leads to the 'clouding' and 'entwining' of the nanoplatelets by the hard segmental chains. This is the first visual evidence of nanomaterial filler and polymer matrix interaction and it could open up a spectrum of novel property achievements in nanocomposite thin films. Also the understanding of this interaction can lead to more controlled architecture of nanocomposites.

36 MATERIALS SCIENCE↗