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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Synergizing Electron and Heat Flows in Photocatalyst for Direct Conversion of Captured CO 2

Abstract We report a ternary hybrid photocatalyst architecture with tailored interfaces that boost the utilization of solar energy for photochemical CO 2 reduction by synergizing electron and heat flows in the photocatalyst. The photocatalyst comprises cobalt phthalocyanine (CoPc) molecules assembled on multiwalled carbon nanotubes (CNTs) that are decorated with nearly monodispersed cadmium sulfide quantum dots (CdS QDs). The CdS QDs absorb visible light and generate electron‐hole pairs. The CNTs rapidly transfer the photogenerated electrons from CdS to CoPc. The CoPc molecules then selectively reduce CO 2 to CO. The interfacial dynamics and catalytic behavior are clearly revealed by time‐resolved and in situ vibrational spectroscopies. In addition to serving as electron highways, the black body property of the CNT component can create local photothermal heating to activate amine‐captured CO 2 , namely carbamates, for direct photochemical conversion without additional energy input.

Choi, Chungseok↗
DOE OSTI2023

Synergizing Electron and Heat Flows in Photocatalyst for Direct Conversion of Captured CO 2

We report a ternary hybrid photocatalyst architecture with tailored interfaces that boost the utilization of solar energy for photochemical CO 2 reduction by synergizing electron and heat flows in the photocatalyst. The photocatalyst comprises cobalt phthalocyanine (CoPc) molecules assembled on multiwalled carbon nanotubes (CNTs) that are decorated with nearly monodispersed cadmium sulfide quantum dots (CdS QDs). The CdS QDs absorb visible light and generate electron-hole pairs. The CNTs rapidly transfer the photogenerated electrons from CdS to CoPc. The CoPc molecules then selectively reduce CO 2 to CO. Here, the interfacial dynamics and catalytic behavior are clearly revealed by time-resolved and in situ vibrational spectroscopies. In addition to serving as electron highways, the black body property of the CNT component can create local photothermal heating to activate amine-captured CO 2 , namely carbamates, for direct photochemical conversion without additional energy input.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Hybrid Carbon Dioxide Reduction Photocatalysts Consisting of Macrocyclic Cobalt(III) Complexes Deposited on Semiconductor Surfaces

Hybrid photocatalysts can be prepared by coupling metal ligand complexes with light-harvesting semiconductors. It is often challenging and time consuming to derivatize ligands with anchoring groups to effectively attach onto surfaces. In this study, we synthesized hybrid carbon dioxide reduction photocatalysts by directly depositing two macrocyclic Co(III) complexes on three different semiconductor surfaces (TiO 2 , N-Ta 2 O 5 and C 3 N 4 ). The resulting hybrid photocatalysts were characterized with various techniques and tested in CO 2 reduction reactions under different light conditions. Excellent visible-light CO 2 -reduction activity was obtained using C 3 N 4 as the light-harvesting semiconductor. Furthermore, density functional theory calculations were conducted to help understand interactions between the cobalt complexes with a model TiO 2 surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Recent advances in rational design of defect-engineered photocatalysts toward sustainable NH 3 synthesis as H 2 carrier: From fundamental and development to machine-learning

In this study, we provide a detailed overview of the fundamental mechanisms underpinning photocatalytic N 2 reduction. We also discuss advances in catalyst design for the synthesis of NH 3 . Particular emphasis is placed on the role of surface defect engineering, which includes the creation of surface defects to enhance the performance of semiconducting photocatalysts for efficient N 2 reduction. In addition, the application of a machine learning-based computational modeling approach is discussed as an important driving force for predicting and regulating NH 3 synthesis efficiency based on catalyst features and reaction conditions. Finally, existing challenges and future perspectives for improving the performance of defect-engineered photocatalysts are outlined to contribute to the ongoing discourse on sustainable ammonia generation. This review aims to clarify recent progress in the rational design of defect-containing photocatalysts for the synthesis of NH 3 and encourages innovative approaches to catalyst optimization rather than solely focusing on new materials.

08 HYDROGEN↗
DOE OSTI2022

Stable and Recyclable Photocatalysts of CsPbBr 3 @MSNs Nanocomposites for Photoinduced Electron Transfer RAFT Polymerization

All-inorganic metal halide perovskite CsPbX 3 (X = Cl, Br, I) nanocrystals (NCs) have demonstrated attractive optoelectronic characteristics. However, their photocatalytic properties are limited by their poor stability and easy recombination of photogenerated carriers. Herein, we introduced a CsPbBr 3 @MSNs nanocomposite (CsPbBr 3 NCs embedded in dendritic mesoporous silica nanospheres (MSNs)) as photocatalysts for photoinduced electron transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. In this study, the CsPbBr 3 nanocrystals (~8.1 nm; PLQY of 62 ± 2.1%) were embedded in dendritic MSNs using a nanoconfinement strategy. PET-RAFT polymerization was successfully initiated using the CsPbBr 3 @MSNs nanocomposite as the photocatalyst. Reaction variables, such as catalyst loading, monomer composition, and excitation light wavelengths, were varied to yield polymers with the desired control of molecular weight and dispersity as well as block copolymers with high chain-end fidelity. In addition, the perovskite-based photocatalysts could be readily separated and purified, which allowed effective and rapid recycling of the nanocomposites for multiple polymerization cycles.

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

Revealing the role of redox reaction selectivity and mass transfer in current–voltage predictions for ensembles of photocatalysts

Photocatalysts are conceptually simple reaction units where nanoscale semiconductors integrated with catalysts drive a pair of redox reactions on illumination. However, the proximity of reaction sites performing cathodic and anodic reactions poses dire challenges to realize large light-to-fuel conversion efficiencies. In this study, a powerful, yet straightforward, equivalent-circuit detail-balance modeling framework is developed and applied to evaluate the performance of photocatalytic systems featuring multiple light absorbers. Specifically, low bandgap iridium-doped strontium titanate is modeled as a Z-scheme photocatalyst to achieve desirable hydrogen evolution and iron-based redox shuttle oxidation reactions. Our model has unique capabilities to simulate competing redox reactions and address mass-transfer limitations. In a significant departure from state-of-the-art circuit models, our study develops tools to perform load-line analyses by incorporating a net electrochemical load curve that includes both desired and competing redox reactions. Consequently, reaction selectivity is predicted from equivalent circuit models for photocatalytic and photoelectrochemical systems. Our investigation into ensembles comprised of multiple, semi-transparent light absorbers reveals their potential to outperform a single, optically thick light absorber, particularly when operated under mass-transfer-limited conditions. However, this outcome hinges on minimizing mass-transfer rates of select redox species to prevent undesired reactions of hydrogen oxidation and/or redox shuttle reduction. Our findings demonstrate that reaction selectivity can be achieved by tuning asymmetry in redox species mass-transfer even with perfectly symmetric electrocatalytic charge-transfer coefficients. The influences of various kinetic, mass-transfer, and thermodynamic parameters are explored to offer crucial insights for synthesis of the next-generation of photocatalysts and selective coatings, and reactor designs.

25 ENERGY STORAGE↗
DOE OSTI2020

Photophysical characterization of new osmium (II) photocatalysts for hydrohalic acid splitting

Two osmium(II) photocatalysts bearing a dicationic 4,4'-bis-(trimethylaminomethyl)-2,2'-bipyridine (tmam) ligand and 2,2'-bipyridine {[Os(bpy) 2 (tmam)] 4+ } or 4,4'-(CF 3 ) 2 -2,2'-bipyridine {[Os((CF3)2bpy) 2 (tmam)] 4+ } ancillary ligands were synthesized and characterized for application in HX splitting. Iodide titration studies in acetone solutions provided evidence for an in situ formed terionic complex with two iodide ions as evidenced by 1H NMR and UV-visible absorption spectroscopies, as well as by density functional theory calculations and natural bond order analysis. The photocatalyst [Os(bpy)2(tmam)] 4+ was shown to be inefficient in iodide oxidation. In contrast, visible light excitation of [Os((CF3)2bpy)2(tmam)]4+ led to rapid iodide oxidation, kq = 2.8 × 1011 M-1 s-1. The data reveal that Os(II) photocatalysts can be fine-tuned for application in HX splitting.

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

Development of Metal-Free Photocatalysts

Solar fuels show great promise as clean, sustainable energy sources; however, established technologies are still plagued by high price, toxicity concerns, or low efficiencies. There is a critical need for inexpensive, benign materials that can effectively harness the sun’s energy. The overarching objective of this project is to evaluate the compatibility of novel material combinations for use as metal-free, heterojunction photocatalysts. Our central hypothesis is that by tuning the electronic structure of individual components in hybrid composites, via selective chemical modifications and physical stimuli to the interface, we can improve the photocatalytic properties of the overall assembly. We will determine factors that affect energy band gaps and band edge positions in isolated photocatalyst systems as well as explore routes to modulate heterojunction band alignments in composite assemblies. Our results will predict accessible pathways for charge carriers in new composite photocatalysts, facilitating access to more of the solar spectrum via inexpensive, environmentally-friendly material combinations.

14 SOLAR ENERGY↗
DOE OSTI2024

Ultrathin layer photocatalysts

A transparent ceramic substrate is covered by a photocatalyst layer, at least partially. The photocatalyst layer includes a semiconductor material that, upon exposure to electromagnetic radiation, forms a plurality of electrons and a plurality of holes that remain confined to the photocatalyst layer. The transparent ceramic substrate has a diameter that is larger than the wavelength of the electromagnetic radiation for light trapping.

Wang, Yifeng↗
DOE OSTI2023

Ti‐Modified Imogolite Nanotubes as Promising Photocatalyst 1D Nanostructures for H 2 Production

Imogolite nanotubes (INTs) are predicted as a unique 1D material with spatial separation of conduction and valence band edges but their large band gaps have inhibited their use as photocatalysts. The first step toward using these NTs in photocatalysis and exploiting the polarization-promoted charge separation across their walls is to reduce their band gap. Here, the modification of double-walled aluminogermanate INTs by incorporation of titanium into the NT walls is explored. The precursor ratio x = [Ti]/([Ge]+[Ti]) is modulated between 0 and 1. Structural and optical properties are determined at different scales and the photocatalytic performance is evaluated for H 2 production. Although the incorporation of Ti atoms into the structure remains limited, the optimal condition is found around x = 0.4 for which the resulting NTs reveal a remarkable hydrogen production of ≈1500 µmol g −1 after 5 h for a noble metal-free photocatalyst, a 65-fold increase relative to a commercial TiO 2 -P25. This is correlated to a lowering of the recombination rate of photogenerated charge carriers for the most active structures. These results confirm the theoretical predictions regarding the potential of modified INTs as photoactive nanoreactors and pave the way for investigating and exploiting their polarization properties for energy applications.

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

Toward Spatial Control of Reaction Selectivity on Photocatalysts Using Area-Selective Atomic Layer Deposition on the Model Dual Site Electrocatalyst Platform

Photocatalytic water splitting is a promising route to low-cost, green H 2 . However, this approach is currently limited in its solar-to-hydrogen conversion efficiency. One major source of efficiency loss is attributed to the high rates of undesired side and back reactions, which are exacerbated by the proximity of neighboring oxidation and reduction sites. Nanoscopic oxide coatings have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as it cannot facilitate both half-reactions. In this work, area selective atomic layer deposition (AS-ALD) was used to selectively deposit semipermeable TiO 2 films onto model metallic cocatalysts for enhancing reaction selectivity while maintaining a high overall activity. Pt and Au were used as exemplary reduction and oxidation cocatalyst sites, respectively, where Au was deactivated toward ALD growth through self-assembled thiol monolayers while TiO 2 was coated onto Pt sites. Electroanalytical measurements of monometallic thin film electrodes showed that the TiO 2 -encapsulated Pt effectively suppressed undesired H 2 oxidation and Fe(II)/Fe(III) redox reactions while still permitting the desired hydrogen evolution reaction (HER). A planar model photocatalyst platform containing patterned interdigitated arrays of Au and Pt microelectrodes was further assessed using scanning electrochemical microscopy (SECM), demonstrating the successful use of AS-ALD to enable local reaction selectivity in a dual-reaction-site (photo)electrocatalytic system. Finally, interdigitated microelectrodes having independent potential control were used to show that selectively deposited TiO 2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared with uncoated control samples.

08 HYDROGEN↗
DOE OSTI2025

Polymer nanoparticle photocatalysts realized in non-aqueous solvents

Colloidal organic nanoparticles (oNPs) have emerged as a promising category of photocatalyst, thanks to their long-lived surface-bound charges, electronic tunability, and strong absorption in the visible spectrum. Our previous research has established a direct correlation between charge generation in oNPs and their photocatalytic activity, highlighting their effectiveness as a framework for stable, long-lived free carriers. However, oNPs have been restricted to use only in aqueous environments as a result of being synthesized via either nano-emulsion or nano-precipitation procedures. Herein, we present a method for transferring oNP photocatalysts from water into polar non-aqueous solvents while retaining their long-term colloidal stability. We observed that the polymer chains in the solvent-transferred oNPs rearrange from a predominantly H-aggregate structure in water to a combination of H- and J-aggregate characteristics in N,N-dimethylformamide, suggesting a dynamic rearrangement in response to the new solvent environment. Importantly, transient absorption and time-resolved microwave conductivity measurements confirm that the solvent-transferred oNPs maintain their ability to generate free charges at an internal heterojunction. This development opens unique opportunities for eventually leveraging light-generated, long-lived electrons and holes in synthetic redox chemistry across diverse solvent environments, a direction that will be explored in future studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Towards Spatial Control of Reaction Selectivity on Photocatalysts using Area Selective Atomic Layer Deposition on Model Dual Site Electrocatalyst Platform

Photocatalytic water splitting is a promising route to low-cost H2; however, this approach is currently limited by solar-to-hydrogen (STH) conversion efficiencies in the sub-10% range. Z-scheme water splitting, in which H2 and O2 evolving particles are operated in separate compartments and electronically coupled by a soluble redox mediator, offers improvements in STH efficiency but introduces high rates of undesired side and back reactions. Nanoscopic oxide coatings (e.g., CrOx, and SiOx) have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as the particle can no longer facilitate both half reactions. In contrast to photodeposition, which may produce non-uniform overlayers due to the difficulty of controlling local electrochemical reactivity on the surface, area-selective atomic layer deposition (AS-ALD) can be used to deposit conformal ultrathin oxide coatings while preserving access to non-growth areas of a substrate surface. To develop this technique for Z-scheme photocatalysts, we performed AS-ALD of TiO2 on a dual site planar electrocatalyst based on interdigitated arrays of Pt and Au. Self-assembled monolayers of 1-octadecanethiol (ODT) were used to block growth on the Au array, resulting in a patterned surface in which only the Pt sites were encapsulated with TiO2. These electrocatalysts demonstrated localized reaction selectivity for hydrogen evolution reaction (HER) over the TiO2/Pt sites, while the uncoated Au sites retained activity towards Fe(II)/Fe(III) redox (FeRR). Under independent potential control, these microelectrodes showed that selectively deposited TiO2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared to uncoated control samples.

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

Charge Concentration Limits the Hydrogen Evolution Rate in Organic Nanoparticle Photocatalysts

Colloidal organic nanoparticles have proven to be a promising class of photocatalyst for performing the Hydrogen Evolution Reaction (HER) due to their dispersibility in aqueous environments, their strong absorption within the visible region, and the tunabilty of their component materials' redox potentials. Currently, there is little understanding of how charge generation and accumulation in organic semiconductors change when these materials are formed into nanoparticles that share a high interfacial area with water, nor is it known what mechanism limits the hydrogen evolution efficiency in recent reports on organic nanoparticle photocatalysts. Herein, we use Time-Resolved Microwave Conductivity to study aqueous-soluble organic nanoparticles and bulk thin films composed of various blend ratios of the non-fullerene acceptor EH-IDTBR and conjugated polymer PTB7-Th and examine the relationship between composition, interfacial surface area, charge carrier dynamics, and photocatalytic activity. We quantitatively measure the rate of Hydrogen Evolution Reaction by nanoparticles composed of various donor:acceptor blend ratio compositions and find that the most active blend ratio displays a Hydrogen Quantum Yield of 0.83% per photon. Moreover, we find that nanoparticle photocatalytic activity corresponds directly to charge generation, and that nanoparticles have 3x more long-lived accumulated charges relative to bulk samples of the same material composition. Here these results suggest that, under our current reaction conditions, with approximately 3x solar flux, catalytic activity by these nanoparticles is limited by the concentration of electrons and holes in operando and not a finite number of active surface cites or the catalytic rate at the interface. This provides a clear design goal for the next generation of efficient photocatalytic nanoparticles.

08 HYDROGEN↗
DOE OSTI2023

Effects of Anionic Polymer Modification of Dye‐Sensitized Niobate Photocatalysts on Solar‐Driven Z‐Scheme Overall Water Splitting

Pt‐intercalated calcium niobate nanosheets (Pt/HCa 2 Nb 3 O 10 ) sensitized by a Ru(II) complex dye are good photocatalysts for producing H 2 from aqueous solutions containing I − as a reversible electron donor. These materials are applicable to Z‐scheme overall water splitting in combination with a WO 3 ‐based O 2 ‐evolving photocatalyst under simulated sunlight. In this work, the effects of anionic polymer modification of the dye‐sensitized nanosheets are examined by adsorbing sodium poly(styrenesulfonate) (PSS), sodium polyacrylate, sodium polymethacrylate (PMA), or sodium poly(4‐styrenesulfonic‐ co ‐maleic acid) onto the dye‐sensitized nanosheet surface. For half‐cell H 2 ‐evolution reaction in the presence of NaI, all of the polymers have a positive impact on the activity under visible light at lower light intensity, whereas only PMA is effective under high light‐intensity condition. For Z‐scheme overall water splitting with PtO x /H‐Cs‐WO 3 , PSS and PMA give almost the same solar‐to‐hydrogen energy conversion efficiencies (0.12% ± 0.01%) under optimized conditions. However, PMA operates better than PSS at relatively low and high NaI concentrations, which are in general disadvantageous for the H 2 ‐ and O 2 ‐evolving components of the Z‐scheme, respectively.

Energy & Fuels↗
DOE OSTI2022

Transition-metal doped titanate nanowire photocatalysts boosted by selective ion-exchange induced defect engineering

Defect engineering through elemental doping is an efficient way to boost the performance of semiconductor photocatalysts. For this work, transition-metal (TM) doped titanate nanowires (TNWs) were prepared via ion-exchange over the titanate precursors and demonstrated for the Rhodamine B (RhB) degradation under ultraviolet (UV) light irradiation. The ion-exchange of selective ions (V 5+ , Cr 3+ , Ni 2+ , and Zn 2+ ) with protons from pristine TNWs resulted in the hierarchical meso-porosity of nanowires with large pores of ~5–20 nm by TM doping and small pores of ~3.6–4.5 nm inherited from pristine TNWs, which facilitates the mass transfer while maintaining high surface area and active sites. Meanwhile, the TM intercalation partially reduces the Ti 4+ to Ti 3+ and narrows the optical bandgap, which, together with oxygen vacancies and superoxide radicals from pristine TNWs, enhance the adsorption and photocatalytic degradation performance of RhB. This work helps to elucidate the effects of transition-metal doping and provides a rational strategy towards high performance titanate-based photocatalysts for efficient and sustainable wastewater treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electronic Structure Tuning of Lanthanidocene Photocatalysts for C–F Bond Cleavage

A set of nine new robust, tunable cerium complexes supported by an ansa-bis(cyclopentadienyl) ligand, [Me 2 Si(η 5 -Cp R ) 2 ]CeX ( an Cp R )CeX, are excellent homogeneous visible-light photocatalysts for the monodefluoroalkylation of trifluorotoluene with Mg(CH 2 C 6 H 5 ) 2 THF 2 (R = Me 4 , SiMe 3 , X = N(SiMe 3 ) 2 (N″), X = CH(SiMe 3 ) 2 (R''), Cl, OC 6 H 2 t Bu 2 -2,6,Me-4 (OAr)). The trends in photocatalytic activity within the series are explained by photophysical spectroscopic analyses. The aryloxide complex [Me 2 Si(Cp SiMe3 ) 2 ]CeOAr, which has the highest activity (95% substrate conversion in 27 h), shows the most negative (most reducing) excited-state reduction potential (-2.71 V vs Fc). The precatalyst excited-state lifetimes are also exceptionally long. Detailed photoluminescence, NMR spectroscopic, and kinetic studies on chloride [Me 2 Si(Cp Me4 ) 2 ]CeCl suggest that the "ate" complex [{Me 2 Si(Cp Me4 ) 2 } 2 Ce III ClBn][MgBn] is the active catalyst in the alkylation reaction to form PhCF 2 CH 2 Ph with high selectivity over PhCF 2 H. Finally, the reaction rates are up to 30 times higher than previously reported for organometallic rare-earth photocatalysts for these Ce complexes and comparable to established Ir-based photoredox systems.

catalysts↗
DOE OSTI2024

Excited State Bond Homolysis of Vanadium(V) Photocatalysts for Alkoxy Radical Generation

Advancements in photocatalysis have transformed synthetic organic chemistry, using light as a powerful tool to drive selective chemical transformations. Recent approaches have focused on metal-halide ligand-to-metal charge transfer (LMCT) photoactivated bond homolysis reactions leveraged by earth-abundant elements to generate valuable synthons for radical-mediated cross-coupling reactions. Of recent utility, oxovanadium(V) LMCT photocatalysts exhibit selective alkoxy radical generation from aliphatic alcohols upon blue light (UVA) irradiation under mild conditions. The selective photochemical liberation of alkoxy radicals is valuable for applying late-stage fragmentation approaches in organic synthesis and depolymerization strategies for nonbiodegradable polymers. Steady-state and time-resolved spectroscopy were used to assign the electronic structure of three well-defined V(V) photocatalysts in their ground and excited states. We assign the excited state for this transformation at earth-abundant vanadium(V), interrogating the electronic structure using static UV–visible absorption, ultrafast transient absorption, and electron paramagnetic resonance spectroscopy coupled to computational approaches. Furthermore, these findings afford assignments of the short-lived excited state intermediates that dictate selective homolytic bond cleavage in metal alkoxides, illustrating the valuable insight gleaned from fundamental investigations of the molecular photochemistry responsible for light-escalated chemical transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗