Engineering topics

Zhang, Jian

Publications and source records attributed to Zhang, Jian.

10 records

DOE OSTI2026

Regulation of Energy and Mass Transport in a Hydrogen-Bonded Framework for Visible-Light-Driven CO2 Reduction in Water

Photoenzymatic reduction of CO2 to formate is a promising strategy for carbon valorization, yet its efficiency is still limited by inefficient energy and mass transport. Here, we design a series of isostructural hydrogen-bonded organic frameworks (HOFs) that establish confinement effects to promote photocatalytic NADH regeneration and the subsequent NADH-dependent enzymatic CO2-to-formate reduction. We demonstrate that spatial confinement within the framework channels localizes exciton migration to nanoscale domains and promotes interfacial dissociation. Additionally, Rh-induced electronic-structure modulation enables ultrafast electron transfer, while the intrinsic hydrogen-bond network furnishes directional proton conduction to NAD+. These synergistic regulations afford a photocatalytic NADH regeneration efficiency of 99.8% with a record apparent quantum efficiency of 32.8%, and drive formate production at a rate of 3020 μmol g-1 h-1 with 100% selectivity─the highest rate reported to date for all light-driven systems in water. The HOF-based catalyst retains 86.3% of its initial activity over five cycles, highlighting its robustness. This work offers mechanistic insight into how microenvironment engineering within HOF architectures regulates energy and mass transport in photoenzymatic catalysis, paving the way for the rational design of advanced hybrid catalytic systems.

Xu, Jiaxing↗

DOE OSTI2026

A Quinoidal Two‐Dimensional Metal–Organic Framework for High‐Performance Micro‐Supercapacitors and Solid‐State Lithium Batteries

Two-dimensional (2D) metal-organic frameworks (MOFs) integrating redox-active linkers enable dense charge sites and open ion pathways for microscale energy storage. We report a quinoidal dicarboxylate ligand, AQM-H2L, derived from p-azaquinodimethane, forming crystalline frameworks with Cu2+ and Zn2+ nodes. The Cu-based MOF (AQM-AQM-H2L-Cu) exhibits layered sheets (>14 Å spacing) constructed from dinuclear Cu-carboxylate units and conjugated AQM linkers, which narrow the bandgap and introduce Cu2+/Cu+ pseudocapacitance. Exfoliated nanosheets (∼5 nm) retain crystallinity and excellent processability. Integrated into graphene films, they deliver areal and volumetric capacitances of 29.6 mF cm-2 and 18.1 F cm-3, achieving 2.6 mWh cm-3 energy density at 160 mW cm-3. As ionic fillers (1 wt%) in PEO solid polymer electrolytes, the nanosheets markedly enhance LiFePO4 cell performance, affording 169.8 mAh g-1 at 0.2 C and 93% retention after 400 cycles. This work establishes quinoidal linkers as a compact and robust design motif for ionically active 2D frameworks toward high-performance miniature and solid-state energy devices.

Chen, Ziman↗

DOE OSTI2026

Lewis Acid‐Activated Charge Trapping in Dielectric Polymers for Superior High‐Temperature Electrostatic Energy Storage

Dielectric polymer capacitors are essential for electrostatic energy storage but suffer from charge transport-induced energy losses, particularly at elevated temperatures where thermally activated charge carriers exacerbate conduction. Conventional mitigation strategies rely on introducing heterogeneous interfaces to create charge traps, complicating scalable film fabrication. A homogeneous molecular trapping mechanism would circumvent these complexities, yet remains underexplored. Herein, a charge trapping strategy is devised by modifying the lowest occupied molecular orbitals of dielectric polymers through Lewis acid-base adduct formation. The use of tris(pentafluorophenyl)boron (BCF) as a Lewis acidic molecular additive introduces deeper charge traps in commercial polyetherimide (PEI) while retaining homogeneity. With only 0.5 wt.% loading, the PEI-BCF film exhibits greatly improved breakdown strength, achieving an ultrahigh discharged energy density of 7.3 J cm-3 with excellent cycle stability at 200 °C. This work establishes a facile molecular approach to decoupling charge trapping from heterogeneous interfaces, enabling high-energy-density polymer capacitors operable under extreme thermal conditions.

Fan, Lu↗

DOE OSTI2025

Ultrafast Electron–Dipole Interactions in TeO- Photodetachment

We present direct experimental evidence of ultrafast coupling between ejected electrons and dynamically forming dipole moments in TeO, captured during the photodetachment of TeO?. By combining high-resolution cryogenic photoelectron spectroscopy with velocity-map imaging, we assess previously inaccessible excited states and resolve rich photoelectron angular distributions (PADs) that encode electron–dipole interactions. Systematic comparison of PADs from femtosecond and picosecond lasers reveals striking deviations from free-electron behavior, representing direct evidence of a transient dipole moment evolving on femtosecond timescales. Quantitative analysis pinpoints the dipole buildup time to be within ~60 fs, providing real-time access to the birth of a molecular dipole field. This work establishes a general approach to probing electron-dipole interactions in their formation stages, offering fundamental insights into the ultrafast interplay between departing electrons and transient polar systems — a process that lies at the core of atomic, molecular, and ultrafast physics.

Yang, Fan↗

DOE OSTI2025

Reuniting crystallography with real space: Ab initio structure elucidation with 4D-STEM

Structure elucidation via single-crystal methods has historically lacked experimental access to real-space information, instead relying exclusively on diffraction-space measurements of Bragg reflections. Here we exploit the dual-space imaging power of 4D scanning transmission electron microscopy to meaningfully integrate real-space information into the crystallographic workflow. We show that virtual apertures assembled by segmentation of high-angle annular dark-field images enable i) pixel-by-pixel separation of coherent Bragg signal from clusters of closely spaced nanocrystals and ii) selective extraction of integrated intensities from thinner subregions of individual specimens, facilitating retroactive tuning of multiple scattering artifacts. This strategy empowers us to simply pick and choose whichever nanoscale regions of interest generate the highest-quality diffraction patterns, allowing us to solve several independent structures of the metal-organic framework UiO-66 from specimens whose agglomerated morphology proved intractable for conventional microcrystal electron diffraction. Our method is compatible with both rotational and serial approaches to data processing, ultimately divulging the first scanning nanobeam electron diffraction structures determined by direct methods at subangstrom resolution.

Saha, Ambarneil↗

DOE OSTI2025

Human IgE monoclonal antibodies define two unusual epitopes trapping dog allergen Can f 1 in different conformations

Abstract Molecular analysis of interactions between IgE antibody and allergen allows the structural basis of IgE recognition to be defined. Human IgE (hIgE) epitopes of respiratory lipocalin allergens, including Can f 1, remain elusive due to a lack of IgE‐allergen complexes. This study aims to map the structure of allergenic epitopes on Can f 1. The fragment antigen‐binding (Fab) regions of Can f 1 specific human IgE monoclonal antibodies (hIgE mAb) were used to determine the structures of IgE epitopes. Epitope mutants were designed to target Can f 1 epitopes. Immunoassays and a human FcεRIαtransgenic mouse model of passive anaphylaxis in vivo were used to assess the functional activity of epitope mutants. Crystal structures of natural or recombinant Can f 1 complexed with two hIgE mAb 1J11 and 12F3 Fabs, respectively, were determined. The hIgE mAb bound to two partially overlapping epitopes and recognized two different Can f 1 conformations. The hIgE mAb 12F3 showed an unusual mode of binding by protruding its heavy chain CDR3 inside the Can f 1 calyx. Epitope mutants generated based on the structural analyses displayed a 64%–89% reduction in IgE antibody binding and failed to induce passive anaphylaxis in a human FcεRIαtransgenic mouse model. In summary, the structures of Can f 1‐hIgE Fab complexes revealed two unique and partially overlapping epitopes on Can f 1. The modification of the identified IgE epitopes provides a pathway for the design of hypoallergens to treat dog allergies.

Biochemistry & Molecular Biology↗

DOE OSTI2025

Manipulating Aromaticity to Redirect Topochemical Polymerization Pathways

Topochemical polymerization (TCP) represents an essential route to create regio- and stereoregular polymers through solid-state transformations. Herein, we present an innovative strategy for controlling topochemical polymerization pathways by tailoring the terminal group aromaticity in the para-azaquinodimethane (AQM) ring system. Substituting phenyl groups with less aromatic furyl units extends significant spin density delocalization across the conjugated core upon thermal activation, inducing significant diradicaloid characters at furyl positions and enabling unconventional reactivities in both solution and solid states. Thermal treatment in toluene yields a unique cyclophane dimer formed via furyl-methine C-C coupling, confirmed by X-ray crystallography, while solid-state reactions produce polymers formed via both intercolumnar furyl-methine coupling and intracolumnar methine-methine coupling. The spin-center-directed mechanism underlying these transformations is validated through theoretical modeling and isotopic labeling experiments. This study highlights the prowess of aromaticity modulation in functional pro-aromatic systems, which enables the synthesis of polymers with main chain structures that are otherwise difficult to access.

Zhang, Qingsong↗

DOE OSTI2025

PubChemLite Plus Collision Cross Section (CCS) Values for Enhanced Interpretation of Nontarget Environmental Data

Finding relevant chemicals in the vast (known) chemical space is a major challenge for environmental and exposomics studies leveraging nontarget high resolution mass spectrometry (NT-HRMS) methods. Chemical databases now contain hundreds of millions of chemicals, yet many are not relevant. This article details an extensive collaborative, open science effort to provide a dynamic collection of chemicals for environmental, metabolomics, and exposomics research, along with supporting information about their relevance to assist researchers in the interpretation of candidate hits. The PubChemLite for Exposomics collection is compiled from ten annotation categories within PubChem, enhanced with patent, literature and annotation counts, predicted partition coefficient (logP) values, as well as predicted collision cross section (CCS) values using CCSbase. Monthly versions are archived on Zenodo under a CC-BY license, supporting reproducible research, and a new interface has been developed, including historical trends of patent and literature data, for researchers to browse the collection. This article details how PubChemLite can support researchers in environmental and exposomics studies, describes efforts to increase the availability of experimental CCS values, and explores known limitations and potential for future developments. The data and code behind these efforts are openly available.

PubChem↗

DOE OSTI2024

Navigating the Use of Direct Current in Residential Settings: Merits and Obstacles

This review paper provides an in-depth analysis of the role of Direct Current (DC) power systems in residential settings, focusing on their safety, efficiency, and environmental advantages. It recognizes the significant contribution of the residential sector to global carbon dioxide emissions and explores how DC power systems can help mitigate these effects. The paper traces the historical evolution of DC power, its resurgence with renewable energy technologies, and the advancements in power electronics that facilitate its integration. Emphasizing the efficiency and safety benefits, especially in low-voltage applications, the paper highlights the seamless integration of DC systems with inherently DC-generating renewable sources like solar PV and wind. The review discusses the critical role of converter technologies in the transition to DC power and examines the compatibility of DC systems with energy storage solutions, underscoring their potential for enhanced energy management. It also addresses the environmental impacts of adopting DC power, aligning with global carbon reduction efforts. The paper analyzes regional case studies, exploring practical applications and outcomes, and addresses challenges such as the need for standardization. It concludes with recommendations for stakeholders and future research directions, emphasizing the economic, technological, and environmental aspects of DC power systems. Overall, the paper presents DC power as a viable and sustainable option for residential energy conservation, contingent upon ongoing technological progress, supportive policies, and standardization.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

NASA NTRS2016

Evaluating the Impact of Data Placement to Spark and SciDB with an Earth Science Use Case

We investigate the impact of data placement for two Big Data technologies, Spark and SciDB, with a use case from Earth Science where data arrays are multidimensional. Simultaneously, this investigation provides an opportunity to evaluate the performance of the technologies involved. Two datastores, HDFS and Cassandra, are used with Spark for our comparison. It is found that Spark with Cassandra performs better than with HDFS, but SciDB performs better yet than Spark with either datastore. The investigation also underscores the value of having data aligned for the most common analysis scenarios in advance on a shared nothing architecture. Otherwise, repartitioning needs to be carried out on the fly, degrading overall performance.

Spark↗