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Machan, Charles W.

Publications and source records attributed to Machan, Charles W..

17 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Photoluminescence Switching in Quantum Dots Connected with Carboxylic Acid and Thiocarboxylic Acid End-Group Diarylethene Molecules

We contrast the switching of photoluminescence (PL) of PbS quantum dots (QDs) cross-linked with photochromic diarylethene molecules with different end groups, 4,4′-(1-cyclopentene-1,2-diyl)bis[5-methyl-2-thiophenecarboxylic acid] ( 1C ) and 4,4′-(1-cyclopentene-1,2-diyl)bis[5-methyl-2-thiophenethiocarboxylic acid] ( 2T ). Our results show that the QDs cross-linked with the carboxylic acid end group molecules ( 1C ) exhibit a greater amount of switching in photoluminescence intensity compared to QDs cross-linked with the thiocarboxylic acid end group ( 2T ). We also demonstrate that regardless of the molecule used, greater switching amounts are observed for smaller quantum dots. Varying these parameters allows for the fabrication of photoswitches with tunable PL change. We relate these observations to the differences in the HOMO energy levels between the QDs and the photochromic molecules. Our findings demonstrate how the size of the QDs and the energy levels of the linker ligands influences the charge tunneling rate and thus the PL switching performance in tunneling-based photoswitches.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Pre-equilibrium reactions involving pendent relays improve CO 2 reduction mediated by molecular Cr-based electrocatalysts

Homogeneous earth abundant transition-metal electrocatalysts capable of carbon dioxide (CO 2 ) reduction to generate value-added chemical products are a possible strategy to minimize rising anthropogenic CO 2 emissions. Previously, it was determined that Cr-centered bipyridine-based N 2 O 2 complexes for CO 2 reduction are kinetically limited by a proton-transfer step during C–OH bond cleavage. Therefore, it was hypothesized that the inclusion of pendent relay groups in the secondary coordination sphere of these molecular catalysts could increase their catalytic activity. Here, it is shown that the introduction of a pendent methoxy group favorably impacts a pre-equilibrium protonation prior to the catalytic resting state, resulting in a significant increase in catalytic activity without a loss of product selectivity for generating carbon monoxide (CO) from CO 2 . Interestingly, combining the pendent methoxy group with a cationic acid causes a positive shift of the catalytic reduction potential of the system, while maintaining increased activity and quantitative selectivity. This work suggests that tuning the secondary coordination sphere with respect to cationic proton sources can result in activity improvements by modifying the kinetic and thermodynamic aspects of proton transfer in the catalytic cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

The fabrication of polymer-MOF composite gels holds great potential to provide emergent properties for drug delivery, environmental remediation, and catalysis. To leverage the full potential of these composites, we investigated how the presence and chemistry of polymers impact MOF formation within the composites and, in turn, how MOFs impact polymer gelation. We show that polymers with a high density of strongly metal-binding carboxylic acids inhibit MOF formation; however, reducing the density of carboxylic acids or substituting them with weaker metal-binding hydroxyl groups permits both MOF formation and gelation within composites. Preparing composites with poly(ethylene glycol) (PEG), which does not bind MOF zirconium (Zr)-oxo clusters, and observing gelation suggests that MOFs can entrap polymer chains to create cross-links in addition to cross-linking them through polymer-Zr-oxo interactions. Both simulations and experiments show composite hydrogels formed with poly(vinyl alcohol) (PVA) to be more stable than those made with PEG, which can reptate through MOF pores upon heating. We demonstrate the generalizability of this composite formation process across different Zr-based MOFs (UiO-66, NU-901, UiO-67, and MOF-525) and by spin-coating gels into conformable films. PVA-UiO-66 composite hydrogels demonstrated high sorption and sustained release of methylene blue relative to the polymer alone (3× loading, 28× slower release), and PVA-MOF-525 composite hydrogels capably sorb the therapeutic peptide Angiotensin 1–7. By understanding the influence of polymer-MOF interactions on the structure and properties of composite gels, this work informs and expands the design space of this emerging class of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Comparisons of bpy and phen Ligand Backbones in Cr-Mediated (Co-)Electrocatalytic CO 2 Reduction

Due to the rise in atmospheric carbon dioxide (CO 2 ) concentrations, there is a need for the development of new strategies to enhance the selectivity and activity of the electrocatalytic conversion of CO 2 to value-added products. The incorporation of redox mediators (RMs) as co-catalysts to enhance the transfer of redox equivalents during catalysis has been gaining more attention in recent years across a variety of small molecule transformations. We have shown that using Cr-centered complexes with sulfone-based RMs leads to an enhancement of CO 2 reduction electrocatalysis under protic conditions via an inner-sphere mechanism. In these co-catalytic systems, an oxygen atom of the reduced RM binds to the Cr center to form a key intermediate stabilized by pancake bonding between the reduced aromatic components of the catalyst ligand backbone and the RM. This interaction facilitates the transfer of an electron and accesses a more kinetically favorable reaction pathway. Here, we show that expanding the aromatic character of the ligand backbone of the catalyst as well as the RM can cause a greater enhancement of co-electrocatalytic activity. These results suggest that further activity improvements can be achieved by focusing on the kinetic and thermodynamic parameters which control association between the catalyst and RM.

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

Redox Mediators in Homogeneous Co-electrocatalysis

Homogeneous electrocatalysis has been well studied over the past several decades for the conversion of small molecules to useful products for green energy applications or as chemical feedstocks. However, in order for these catalyst systems to be used in industrial applications, their activity and stability must be improved. In naturally occurring enzymes, redox equivalents (electrons, often in a concerted manner with protons) are delivered to enzyme active sites by small molecules known as redox mediators (RMs). Inspired by this, co-electrocatalytic systems with homogeneous catalysts and RMs have been developed for the conversion of alcohols, nitrogen, unsaturated organic substrates, oxygen, and carbon dioxide. In these systems, the RMs have been shown to both increase the activity of the catalyst and shift selectivity to more desired products by altering catalytic cycles and/or avoiding high-energy intermediates. However, the area is currently underdeveloped and requires additional fundamental advancements in order to become a more general strategy. Furthermore, we summarize the recent examples of homogeneous co-electrocatalysis and discuss possible future directions for the field.

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

Mediated Inner‐Sphere Electron Transfer Induces Homogeneous Reduction of CO 2 via Through‐Space Electronic Conjugation**

Abstract The electrocatalytic reduction of CO 2 is an appealing method for converting renewable energy sources into value‐added chemical feedstocks. We report a co‐electrocatalytic system for the reduction of CO 2 to CO comprised of a molecular Cr complex and dibenzothiophene‐5,5‐dioxide (DBTD) as a redox mediator, which achieves high activity (TOF=1.51–2.84×10 5 s −1 ) and quantitative selectivity. Under aprotic or protic conditions, DBTD produces a co‐electrocatalytic response with 1 by coordinating trans to the site of CO 2 binding and mediating electron transfer from the electrode with quantitative efficiency for CO. This assembly is reliant on through‐space electronic conjugation between the π frameworks of DBTD and the bpy fragment of the catalyst ligand, with contributions from dispersive interactions and weak sulfone coordination.

Hooe, Shelby L.↗
DOE OSTI2021

Mediated Inner–Sphere Electron Transfer Induces Homogeneous Reduction of CO 2 via Through–Space Electronic Conjugation

The electrocatalytic reduction of CO 2 is an appealing method for converting renewable energy sources into value-added chemical feedstocks. We report a co-electrocatalytic system for the reduction of CO 2 to CO comprised of a molecular Cr complex and dibenzothiophene-5,5-dioxide (DBTD) as a redox mediator, which achieves high activity (TOF=1.51–2.84×10 5 s –1 ) and quantitative selectivity. Under aprotic or protic conditions, DBTD produces a co-electrocatalytic response with 1 by coordinating trans to the site of CO 2 binding and mediating electron transfer from the electrode with quantitative efficiency for CO. Furthermore, this assembly is reliant on through-space electronic conjugation between the π frameworks of DBTD and the bpy fragment of the catalyst ligand, with contributions from dispersive interactions and weak sulfone coordination.

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

Pendent Relay Enhances H 2 O 2 Selectivity during Dioxygen Reduction Mediated by Bipyridine-Based Co–N 2 O 2 Complexes

Generally, cobalt–N 2 O 2 complexes show selectivity for hydrogen peroxide during electrochemical dioxygen (O 2 ) reduction. We recently reported a Co(III)–N 2 O 2 complex with a 2,2'-bipyridine-based ligand backbone which showed alternative selectivity: H 2 O was observed as the primary reduction product from O 2 (71 ± 5%) with decamethylferrocene as a chemical reductant and acetic acid as a proton donor in methanol solution. We hypothesized that the key selectivity difference in this case arises in part from increased favorability of protonation at the distal O position of the key intermediate Co(III)–hydroperoxide species. To interrogate this hypothesis, in this study we have prepared a new Co(III) compound that contains pendent –OMe groups poised to direct protonation toward the proximal O atom of this hydroperoxo intermediate. Mechanistic studies in acetonitrile (MeCN) solution reveal two regimes are possible in the catalytic response, dependent on added acid strength and the presence of the pendent proton donor relay. In the presence of stronger acids, the activity of the complex containing pendent relays becomes O 2 dependent, implying a shift to Co(III)–superoxide protonation as the rate-determining step. Interestingly, the inclusion of the relay results in primarily H 2 O 2 production in MeCN, despite minimal difference between the standard reduction potentials of the three complexes tested. EPR spectroscopic studies indicate the formation of Co(III)–superoxide species in the presence of exogenous base, with greater O 2 reactivity observed in the presence of the pendent –OMe groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗