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Matula, Adam J.

Publications and source records attributed to Matula, Adam J..

8 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Surprisingly big linker-dependence of activity and selectivity in CO 2 reduction by an iridium(I) pincer complex

In this work, we report the quantitative electroreduction of CO 2 to CO by a PNP-pincer iridium(I) complex bearing amino linkers in DMF/water. The activity and selectivity of the reduction greatly depend on the choice of linker within the ligand. The complex 3-N is far superior to the analogues with methylene and oxygen linkers, showing higher activity and better selectivity for CO 2 over proton reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Strongly Coupled Phenazine–Porphyrin Dyads: Light-Harvesting Molecular Assemblies with Broad Absorption Coverage

The development of light-harvesting architectures with broad absorption coverage in the visible region continues to be an important research area in the field of artificial photosynthesis. In this work, we introduce a new class of ethynyl-linked panchromatic dyads composed of dibenzophenazines coupled ortho and meta to tetrapyrroles with an anchoring group that can be grafted onto metal oxide surfaces. Quantum chemical calculations and photophysical measurements of the synthesized materials reveal that both of the dibenzophenazine dyads absorb broadly from 300 to 636 nm and exhibit absorption bands different from those of the constituent chromophore units. Moreover, the different points of attachment of dibenzophenazines to tetrapyrroles give different absorption profiles which computations suggest result from differences in the planarity of the two dyads. Applicability of the dyads in artificial photosynthesis systems was assessed by their incorporation and characterization of their performance in dye-sensitized solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2018

High-Energy Charge-Separated States by Reductive Electron Transfer Followed by Electron Shift in the Tetraphenylethylene–Aluminum(III) Porphyrin–Fullerene Triad

A high-potential supramolecular triad (TPE-AlPor ← Im-C 60 ) composed of aluminum(III) porphyrin (AlPor), fullerene (C 60 ), and tetraphenylethylene (TPE) has been constructed. The fullerene and tetraphenylethylene units are bound axially to opposite faces of the porphyrin plane via coordination and covalent bonds, respectively. The ground and excited-state properties of the triad and reference dyads are studied using steady-state and time-resolved spectroscopic techniques. The transient data show that photoexcitation results in charge separation from tetraphenylethylene to the excited singlet state of the porphyrin ( 1 AlPor*), generating a high-energy (2.14 eV) charge-separated state, (TPE) •+ -(AlPor) •– , in toluene. A subsequent electron migration from the AlPor –• to fullerene generates a second high-energy (1.78 eV) charge-separated state (TPE) •+ -AlPor ← Im-(C60) •– . The lifetime of the charge separation is about 25 ns. Here, the high energy stored in the form of charge-separated states along with their reasonable lifetimes makes these donor–acceptor systems potential electron-transporting catalysts to carry out energy-demanding photochemical reactions, especially in artificial photosynthesis for conversion of solar energy into chemical energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO 2 Conversion to CO

Photosynthetic CO 2 fixation is mediated by the enzyme RuBisCo, which employs a nonredox-active metal (Mg 2+ ) to bind CO 2 adjacent to an organic ligand that provides reducing equivalents for CO 2 fixation. Attempts to use porphyrins as ligands in reductive catalysis have typically encountered severe stability issues owing to ligand reduction. Here, a synthetic zinc–bacteriochlorin is reported as an effective and robust electrocatalyst for CO 2 reduction to CO with an overpotential of 330 mV, without undergoing porphyrin-like ligand degradation (or demetalation) even after prolonged bulk electrolysis. The reaction has a CO Faradaic efficiency of 92% and sustains a total current density of 2.3 mA/cm 2 at -1.9 V vs Ag/AgCl. DFT calculations highlight the molecular origin of the observed stability and provide insights into catalytic steps. Here, this bioinspired study opens avenues for the application of bacteriochlorin compounds for reductive electrocatalysis with extended life beyond that seen with porphyrin counterparts.

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

Robust resistive memory devices using solution-processable metal-coordinated azo aromatics

Non-volatile memories will play a decisive role in the next generation of digital technology. Flash memories are currently the key player in the field, yet they fail to meet the commercial demands of scalability and endurance. Resistive memory devices, and in particular memories based on low-cost, solution-processable and chemically tunable organic materials, are promising alternatives explored by the industry. However, to date, they have been lacking the performance and mechanistic understanding required for commercial translation. Here we report a resistive memory device based on a spin-coated active layer of a transition-metal complex, which shows high reproducibility (~350 devices), fast switching (≤30 ns), excellent endurance (~10 12 cycles), stability (>10 6 s) and scalability (down to ~60 nm 2 ). In situ Raman and ultraviolet–visible spectroscopy alongside spectroelectrochemistry and quantum chemical calculations demonstrate that the redox state of the ligands determines the switching states of the device whereas the counterions control the hysteresis. This insight may accelerate the technological deployment of organic resistive memories.

Goswami, Sreetosh↗
DOE OSTI2017

Linker Length-Dependent Electron-Injection Dynamics of Trimesitylporphyrins on SnO 2 Films

Electron-injection dynamics of dye-sensitized photoelectrochemical cells depend on the length of the linker connecting the molecular photosensitizer to the metal oxide electron acceptor. However, systematic studies of the effect of chromophore–oxide distance are scarce. In this work, we present the synthesis, characterization, spectroscopy, and computational modeling of electron-injection dynamics from free-base trimesitylporphyrins with varying linker lengths into tin(IV) oxide (SnO 2 ). In each system, the porphyrin core and metal oxide film remain the same while only the linker binding the porphyrin to the carboxylate anchor group is varied. A length range spanning 8.5–17.2 Å is studied by employing phenylene, biphenylene, terphenylene, and benzanilide groups as the linker. We find a clear correlation between linker length and injection rates, providing insights that will be exploited in the optimization of dye-sensitized photoelectrochemical cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗