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The UDSpace Institutional Repository collects and disseminates research material from the University of Delaware.
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- UDSpace also includes all doctoral dissertations from winter 2014 forward, and all master's theses from fall 2009 forward.
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Recent Submissions
Microflow chemistry and its electrification for sustainable chemical manufacturing
(Chemical Science, 2022-08-06) Chen, Tai-Ying; Wei Hsiao, Yung; Baker-Fales, Montgomery; Cameli, Fabio; Dimitrakellis, Panagiotis; Vlachos, Dionisios G.
Sustainability is vital in solving global societal problems. Still, it requires a holistic view by considering renewable energy and carbon sources, recycling waste streams, environmentally friendly resource extraction and handling, and green manufacturing. Flow chemistry at the microscale can enable continuous sustainable manufacturing by opening up new operating windows, precise residence time control, enhanced mixing and transport, improved yield and productivity, and inherent safety. Furthermore, integrating microfluidic systems with alternative energy sources, such as microwaves and plasmas, offers tremendous promise for electrifying and intensifying modular and distributed chemical processing. This review provides an overview of microflow chemistry, electrification, their integration toward sustainable manufacturing, and their application to biomass upgrade (a select number of other processes are also touched upon). Finally, we identify critical areas for future research, such as matching technology to the scale of the application, techno-economic analysis, and life cycle assessment.
Boosting photocatalytic hydrogen production from water by photothermally induced biphase systems
(Nature Communications, 2021-02-26) Guo, Shaohui; Li, Xuanhua; Li, Ju; Wei, Bingqing
Solar-driven hydrogen production from water using particulate photocatalysts is considered the most economical and effective approach to produce hydrogen fuel with little environmental concern. However, the efficiency of hydrogen production from water in particulate photocatalysis systems is still low. Here, we propose an efficient biphase photocatalytic system composed of integrated photothermal–photocatalytic materials that use charred wood substrates to convert liquid water to water steam, simultaneously splitting hydrogen under light illumination without additional energy. The photothermal–photocatalytic system exhibits biphase interfaces of photothermally-generated steam/photocatalyst/hydrogen, which significantly reduce the interface barrier and drastically lower the transport resistance of the hydrogen gas by nearly two orders of magnitude. In this work, an impressive hydrogen production rate up to 220.74 μmol h−1 cm−2 in the particulate photocatalytic systems has been achieved based on the wood/CoO system, demonstrating that the photothermal–photocatalytic biphase system is cost-effective and greatly advantageous for practical applications.
Nanostructured Block Polymer Electrolytes: Tailoring Self-Assembly to Unlock the Potential in Lithium-Ion Batteries
(Accounts of Chemical Research, 2021-12-07) Ketkar, Priyanka M.; Epps, Thomas H. III
Conspectus
Ion-containing solid block polymer (BP) electrolytes can self-assemble into microphase-separated domains to facilitate the independent optimization of ion conduction and mechanical stability; this assembly behavior has the potential to improve the functionality and safety of lithium-ion batteries over liquid electrolytes to meet future demands (e.g., large capacities and long lifetimes) in various applications. However, significant enhancements in the ionic conductivity and processability of BPs must be realized for BP-based electrolytes to become robust alternatives in commercial devices. Toward this end, the controlled modification of BP electrolytes’ intra-domain (nanometer-scale) and multi-grain (micrometer-scale) structure is one viable approach; intra-domain ion transport and segmental compatibility (related to the effective Flory–Huggins parameter, χeff) can be increased by tuning the ion and monomer-segment distributions, and the morphology can be selected such that the multi-grain transport is less sensitive to grain size and orientation.
To highlight the characteristics of intra-domain structure that promote efficient ion transport, this Account begins by describing the relationship between BP thermodynamics (namely, χeff and the statistical segment length, b, which is indicative of chain stiffness) and local ion concentration. These thermodynamic insights are vital because they inform the selection of synthesis and formulation variables, such as polymer and ion chemistry, polymer molecular weight and composition, and ion concentration, which boost electrolyte performance. In addition to its relationship with local ion transport, χeff is also an important factor with respect to electrolyte processability. For example, a reduced χeff can allow BP electrolytes to be processed at lower temperatures (i.e., lower energy input), with less solvent (i.e., reduced waste), and/or for shorter times (i.e., higher throughput) yet still form desired nanostructures. This Account also examines the impact of electrolyte preparation and processing on the ion transport across nanostructured grains because of grain size and orientation. As morphologies with a 3D-connected versus 2D-connected conducting phase show different sensitivities to conductivity losses that can occur because of the fabrication methods, it is necessary to account for electrolyte processing effects when probing ion transport.
The intra-domain and micrometer-scale structure also can be tuned using either tapered BPs (macromolecules with modified monomer-segment composition profiles between two homogeneous blocks) or blends of BPs and homopolymers, independent of the BP molecular weight and composition, as detailed herein. The application of TBPs or BP/HP blends as ion-conducting materials leads to improved ion transport, reduced χeff, and greater availability of morphologies with 3D connectivity relative to traditional (non-tapered and unblended) BP electrolytes. This feature results from the fact that ion transport is related more closely to the monomer-segment distributions within a domain than the overall nanoscale morphology or average polymer/ion mobilities. Taken together, this Account describes how ion transport and processability are influenced by BP architecture and nanostructural features, and it provides avenues to tune nanoassemblies that can contribute to improved lithium-ion battery technologies to meet future demands.
Direct Integration of Strained-Pt Catalysts into Proton-Exchange-Membrane Fuel Cells with Atomic Layer Deposition
(Advanced Materials, 2021-07-28) Xu, Shicheng; Wang, Zhaoxuan; Dull, Sam; Liu, Yunzhi; Lee, Dong Un; Pacheco, Juan S. Lezama; Orazov, Marat; Vullum, Per Erik; Dadlani, Anup Lal; Vinogradova, Olga; Schindler, Peter; Tam, Qizhan; Schladt, Thomas D.; Mueller, Jonathan E.; Kirsch, Sebastian; Huebner, Gerold; Higgins, Drew; Torgersen, Jan; Viswanathan, Venkatasubramanian; Jaramillo, Thomas Francisco; Prinz, Fritz B.
The design and fabrication of lattice-strained platinum catalysts achieved by removing a soluble core from a platinum shell synthesized via atomic layer deposition, is reported. The remarkable catalytic performance for the oxygen reduction reaction (ORR), measured in both half-cell and full-cell configurations, is attributed to the observed lattice strain. By further optimizing the nanoparticle geometry and ionomer/carbon interactions, mass activity close to 0.8 A mgPt−1 @0.9 V iR-free is achievable in the membrane electrode assembly. Nevertheless, active catalysts with high ORR activity do not necessarily lead to high performance in the high-current-density (HCD) region. More attention shall be directed toward HCD performance for enabling high-power-density hydrogen fuel cells.
Correcting a major error in assessing organic carbon pollution in natural waters
(Science Advances, 2021-04-14) Jiao, Nianzhi; Liu, Jihua; Edwards, Bethanie; Lv, Zongqing; Cai, Ruanhong; Liu,Yongqin; Xiao, Xilin; Wang, Jianning; Jiao, Fanglue; Wang, Rui; Huang, Xingyu; Guo, Bixi; Sun, Jia; Zhang, Rui; Zhang, Yao; Tang, Kai; Zheng, Qiang; Azam, Farooq; Batt, John; Cai, Wei-Jun; He, Chen; Herndl, Gerhard J.; Hill, Paul; Hutchins, David; LaRoche, Julie; Lewis, Marlon; MacIntyre, Hugh; Polimene, Luca; Robinson, Carol; Shi, Quan; Suttle, Curtis A.; Thomas, Helmuth; Wallace, Douglas; Legendre, Louis
Microbial degradation of dissolved organic carbon (DOC) in aquatic environments can cause oxygen depletion, water acidification, and CO2 emissions. These problems are caused by labile DOC (LDOC) and not refractory DOC (RDOC) that resists degradation and is thus a carbon sink. For nearly a century, chemical oxygen demand (COD) has been widely used for assessment of organic pollution in aquatic systems. Here, we show through a multicountry survey and experimental studies that COD is not an appropriate proxy of microbial degradability of organic matter because it oxidizes both LDOC and RDOC, and the latter contributes up to 90% of DOC in high-latitude forested areas. Hence, COD measurements do not provide appropriate scientific information on organic pollution in natural waters and can mislead environmental policies. We propose the replacement of the COD method with an optode-based biological oxygen demand method to accurately and efficiently assess organic pollution in natural aquatic environments.