Engineering topics

Tayal, Akhil

Publications and source records attributed to Tayal, Akhil.

6 records

DOE OSTI2024

Elucidating the Discharge Behavior of Aqueous Zinc Sulfur Batteries in the Presence of Molybdenum(IV) Chalcogenide Catalyst: The Criticality of Interfacial Electrochemistry

The aqueous zinc-sulfur battery holds promise for significant capacity and energy density with low cost and safe operation based on environmentally benign materials. However, it suffers from the sluggish kinetics of the conversion reaction. Here, we highlight the efficacy of molybdenum(IV) sulfide (MoS 2 ) to reduce the overpotential of S-ZnS conversion in aqueous electrolytes and study the discharge products formed at the solid-solid and solid-liquid interfaces using experimental and theoretical approaches. Specifically, the MoS 2 -catalyzed electrochemical conversion reaction is characterized via ex situ X-ray diffraction (XRD), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), Raman spectroscopy, synchrotron-based Mo K-edge X-ray absorption spectroscopy (XAS), and in situ synchrotron-based X-ray computed tomography (XCT). Additionally, operando synchrotron-based S K-edge XAS and X-ray fluorescence (XRF) maps are collected to determine the spatial evolution of sulfur-based species at the electrode-electrolyte interface. Further, coupling the operando S K-edge XAS data with the simulated spectra and fitting the data suggested a possible ZnS 2 intermediate phase.

25 ENERGY STORAGE↗

DOE OSTI2024

Tuning metal-support interactions in nickel–zeolite catalysts leads to enhanced stability during dry reforming of methane

Ni-based catalysts are highly reactive for dry reforming of methane (DRM) but they are prone to rapid deactivation due to sintering and/or coking. In this study, we present a straightforward approach for anchoring dispersed Ni sites with strengthened metal-support interactions, which leads to Ni active sites embedded in dealuminated Beta zeolite with superior stability and rates for DRM. The process involves solid-state grinding of dealuminated Beta zeolites and nickel nitrate, followed by calcination under finely controlled gas flow conditions. By combining in situ X-ray absorption spectroscopy and ab initio simulations, it is elucidated that the efficient removal of byproducts during catalyst synthesis is conducted to strengthen Ni–Si interactions that suppress coking and sintering after 100 h of time-on-stream. Transient isotopic kinetic experiments shed light on the differences in intrinsic turnover frequency of Ni species and explain performance trends. This work constructs a fundamental understanding regarding the implication of facile synthesis protocols on metal-support interaction in zeolite-supported Ni sites, and it lays the needed foundations on how these interactions can be tuned for outstanding DRM performance.

36 MATERIALS SCIENCE↗

DOE OSTI2024

In situ Synchrotron X‐ray Metrology Boosted by Automated Data Analysis for Real‐time Monitoring of Cathode Calcination

Abstract Synchrotron X‐ray‐based in situ metrology is advantageous for monitoring the synthesis of battery materials, offering high throughput, high spatial and temporal resolution, and chemical sensitivity. However, the rapid generation of massive data poses a challenge to on‐site, on‐the‐fly analysis needed for real‐time process monitoring. Here, a weighted lagged cross‐correlation (WLCC) similarity approach is presented for automated data analysis, which merges with in situ synchrotron X‐ray diffraction metrology to monitor the calcination process of the archetypal nickel‐based cathode, LiNiO 2 . The WLCC approach, incorporating variables that account for peak shifts and width changes associated with structural transformations, enables rapid extraction of phase progression within 10 seconds from tens of diffraction patterns. Details are captured, from initial precursors to intermediates and the final layered LiNiO 2 , providing information for agile on‐site adjustments during experiments and complementing post hoc diffraction analysis by offering insights into early‐stage phase nucleation and growth. Expanding this data‐powered platform paves the way for real time calcination process monitoring and control, which is pivotal to quality control in battery cathode manufacturing.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Snowflake relocated Cu 2 O electrocatalyst on an Ag backbone template for the production of liquid C 2+ chemicals from CO 2

In this study, we performed the CO 2 reduction reaction (CO 2 RR) using a structural composite catalyst of cuprous oxide (Cu 2 O) and silver (Ag) that was simultaneously electrodeposited. While the underneath Ag electrodeposits maintained their spiky backbone structures even after the CO 2 RR, the Cu 2 O deposits were reduced to Cu(111) and relocated on the backbone template. Here, the structural changes in Cu 2 O to Cu increase the active area of the Cu–Ag interface, resulting in a remarkable production rate of 125.01 μmol h -1 of liquid C 2+ chemicals via the stabilization of the C–C coupling of the key intermediate species of acetaldehyde. This study provides new insights into designing a bimetallic catalyst for producing sustainable C 2+ products from CO 2 without any selectivity towards the production of methane.

36 MATERIALS SCIENCE↗

DOE OSTI2024

In Situ Insights into Cathode Calcination for Predictive Synthesis: Kinetic Crystallization of LiNiO 2 from Hydroxides

Abstract Calcination is a solid‐state synthesis process widely deployed in battery cathode manufacturing. However, its inherent complexity associated with elusive intermediates hinders the predictive synthesis of high‐performance cathode materials. Here, correlative in situ X‐ray absorption/scattering spectroscopy is used to investigate the calcination of nickel‐based cathodes, focusing specifically on the archetypal LiNiO 2 from Ni(OH) 2 . Combining in situ observation with data‐driven analysis reveals concurrent lithiation and dehydration of Ni(OH) 2 and consequently, the low‐temperature crystallization of layered LiNiO 2 alongside lithiated rocksalts. Following early nucleation, LiNiO 2 undergoes sluggish crystallization and structural ordering while depleting rocksalts; ultimately, it turns into a structurally‐ordered layered phase upon full lithiation but remains small in size. Subsequent high‐temperature sintering induces rapid crystal growth, accompanied by undesired delithiation and structural degradation. These observations are further corroborated by mesoscale modeling, emphasizing that, even though calcination is thermally driven and favors transformation towards thermodynamically equilibrium phases, the actual phase propagation and crystallization can be kinetically tuned via lithiation, providing freedom for structural and morphological control during cathode calcination.

36 MATERIALS SCIENCE↗

DOE OSTI2021

A Tunable Multivariate Metal–Organic Framework as a Platform for Designing Photocatalysts

Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO 2 . Recently, metal–organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal–organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB 2 OX 3 bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 mol H2 gcat. –1 min –1 , a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10 –5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗