Search NASA⌕ Search

SEARCH · Search NASA

Results for “Cu formate”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Single‐Crystal to Single‐Crystal Transformations: Stepwise CO 2 Insertions into Bridging Hydrides of [(NHC)CuH] 2 Complexes

Abstract Mechanistic studies of substrate insertion into dimeric [(NHC)CuH] 2 (NHC=N‐heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu−H monomers in solution. Using single‐crystal to single‐crystal (SC‐SC) transformations, we discovered a new pathway of stepwise insertion of CO 2 into [(NHC)CuH] 2 without complete dissociation of the dimer. The first CO 2 insertion into dimeric [(IPr*OMe)CuH] 2 (IPr*OMe=N,N′‐bis(2,6‐bis(diphenylmethyl)‐4‐methoxy‐phenyl)imidazole‐2‐ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐H). A second CO 2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐1,1‐O 2 CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.

Patrick, Evan A.↗
DOE OSTI2021

Dual-atom active sites embedded in two-dimensional C 2 N for efficient CO 2 electroreduction: A computational study

Double-atom catalysts (DACs) have emerged as an enhanced platform of single-atom catalyst for promoting electrocatalytic CO 2 reduction reaction (CO 2 RR). Herein, we present a density-functional theory study on CO 2 RR performance of seven C 2 N-supported homo- and heteronuclear DACs, denoted as M 2 @C 2 N. Our results demonstrate that there exists substantial synergistic effect of dual-metal-atom N 2 M 2 N 2 active site and C 2 N matrix on O&#x2550 C &#x2550O bond activation. The dual-atom M 2 sites are able to drive CO 2 RR beyond C 1 products with low limiting potential (U L ). Specifically, C 2 H 4 formation is preferred on FeM@C 2 N (M = Fe, Co, Ni, Cu) versus CH 4 formation on CuM@C 2 N (M = Co, Ni, Cu). Furthermore, *CO+*CO co-binding strength can serve as a descriptor for CO 2 RR activity for making C 2 products such that the moderate binding results in the lowest U L . Remarkably, C-affinity matters most to C—C bond coupling and C 2 H 4 formation while both C- and O-affinity control CH 4 formation. Furthermore, our results provide theoretical insight into rational design of DACs for efficient CO 2 RR.

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

Mechanistic insights into N 2 O formation as a side product in NH 3 -SCR over small pore Cu-zeolites

Here, the present contribution provides clarity to N 2 O formation mechanisms and key influencing factors during low temperature NH 3 -SCR, with the goal of enabling the rational design of advanced SCR catalysts with low greenhouse gas impact. By studying more than 50 small pore Cu-exchanged zeolite SCR catalyst samples, including model catalysts synthesized in our laboratories and state-of-the-art industrial catalysts, we explored a wide range of factors affecting N 2 O formation. These factors included Cu loading, support Si/Al ratio, support topology, catalyst aging, reaction temperature and reactant feed composition effects. We probed N 2 O formation under both steady-state SCR, and during NH 4 NO 3 decomposition via temperature programmed desorption (TPD). Finally, we used DFT to probe energetics of possible N 2 O formation pathways. Based on these studies, we confirm that low temperature N 2 O formation occurs via multiple reaction pathways that all involve NH 4 NO 3 and are supported by Cu moieties that facilitate in-situ NO oxidation to NO 2 .

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

Cu 2 O/CuS Nanocomposites Show Excellent Selectivity and Stability for Formate Generation via Electrochemical Reduction of Carbon Dioxide

Formate is an important value-added chemical that can be produced via electrochemical CO 2 reduction reactions (CO 2 RR). Cu 2 O-based catalysts have previously demonstrated decent activity for formate generation; however, they often suffer from poor electrochemical stability under reductive conditions. Here, in this paper, we report a new Cu 2 O/CuS composite catalyst that simultaneously achieves an excellent faradaic efficiency of 67.6% and a large partial current density of 15.3 mA/cm 2 at –0.9 V vs RHE for formate. Importantly, it maintains an average faradaic efficiency of 62.9% for at least 30 h at the same potential. The catalytic selectivity and stability for formate production outperform other Cu, CuS, and Cu 2 O catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Anodic Hydrogen Generation from Benzaldehyde on Au, Ag, and Cu: Rotating Ring-Disk Electrode Studies

Aldehydes are selectively oxidized to carboxylates on group 11 metals at low potentials (<0.4 V vs. RHE) in alkaline media. This process can occur by a pathway that generates H 2 gas from the aldehyde, known as electro-oxidative dehydrogenation (EOD) or anodic hydrogen production. The EOD process occurs with transfer of only one electron per aldehyde, whereas typical oxidation with discharge of hydrogen to form water is a two-electron process. Here, we study the catalytic activity and selectivity toward H 2 of Au, Ag, and Cu electrodes using benzaldehyde with rotating disk and ring-disk electrode (RDE/RRDE) techniques. The average number of electrons per benzaldehyde molecule obtained via H 2 detection by RRDE agrees with that obtained via Koutecký-Levich analysis conducted at various rotation rates. We find that Au and Ag have much higher H 2 and benzoate formation rates than Cu, but that Cu can perform the reaction at about 0.2 V lower overpotentials. On all three materials, benzaldehyde oxidation has high selectivity to anodic H 2 (one-electron pathway) below ∼0.5 V vs. RHE, but, with increasing potential, the selectivity shifts to H-oxidation forming water (two-electron pathway).

Ramos, Nathanael C. (ORCID:0000000247210350)↗
DOE OSTI2024

Mechanisms and site requirements for NO and NH 3 oxidation on Cu/SSZ-13

Two series of Cu/SSZ-13 catalysts were synthesized via aqueous solution and solid-state ion exchange using SSZ-13 supports of varying Si/Al ratios. The isolated and multinuclear Cu content of these catalysts were determined by H 2 temperature programmed reduction (H 2 -TPR). Multinuclear Cu in these catalysts, including in situ Cu- dimers formed from ZCu II OH coupling and permanent CuO clusters, are active species for dry NO oxidation. NH 3 oxidation on these catalysts follows an internal SCR (i-SCR) mechanism, i.e., a portion of NH 3 is first oxidized to NO, then NO is selectively reduced by the remaining NH 3 to N 2 . NH 3 oxidation displays distinct kinetic behavior below ~300 °C and above ~400 °C. At low temperature the results indicate that NH 3 -solvated mobile Cu-ions are the active centers. CuO clusters, when present, also contribute to the low temperature activity by catalyzing NH 3 oxidation to NO. At high temperature, in situ Cu-dimers and CuO clusters catalyze NH 3 oxidation to NO, and isolated Cu-ions catalyze SCR to realize the cascade turnovers. For both NO and NH 3 oxidation, Cu-dimers balanced by framework charges of close proximity appear to be more active than Cu-dimers balanced by distant framework charges. However, the former Cu-dimers are less stable than the latter and tend to split into monomers in the presence of vicinal Brønsted acid sites. Via density functional theory (DFT) calculations, the i-SCR mechanism for low temperature NH 3 oxidation, i.e., the energetic favorability for the involvement of the NO intermediate, is justified. Furthermore, the DFT results also agree with experimental data that the formation of Cu-dimers from ZCu II OH dimerization is essential for NH 3 oxidation at high temperature.

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

Twinning Enhances Efficiencies of Metallic Catalysts toward Electrolytic Water Splitting

Twinning is demonstrated to be an effective way of enhancing efficiencies of metallic catalysts toward electrolytic water splitting. Dendritic Cu possessing dense coherent nanotwin (NT) boundaries (NTCu-5nm) is successfully prepared with an organic-assisted electrodeposition at high pulse current densities. NT boundaries significantly improve electrocatalytic efficiencies and stability of NTCu-5nm over nanocrystalline Cu (NCCu), reducing overpotentials at 10 mA cm -2 for the oxygen evolution reaction (OER) from 378 to 281 mV and from 235 to 88 mV for the hydrogen evolution reaction (HER), with a small chronoamperometric decay of 5% after 100 h continuous overall water splitting at an ultrahigh initial current density of 500 mA cm -2 , largely outperforming the large chronoamperometric decay of 27% for only 1 h operation of the NCCu//NCCu couple. The defective twin boundaries enable formation of active Cu III O 2 - at low overpotentials, thus enhancing OER performance. Furthermore, the synergistic geometric and electronic effects induced by the twin boundaries result in shifts in Gibbs free energies of hydrogen adsorption (ΔG H ) toward the apex of a volcano plot of exchange current density versus ΔG H , leading to the remarkable improvement in HER activity.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Binding, Release and Functionalization of Intact Pnictogen Tetrahedra Coordinated to Dicopper Complexes

The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu 2 (μ,η 1 : η 1 -MeCN)][X] 2 (X=weakly coordinating anion, NTf 2 (1 a), FAl[OC 6 F 10 (C 6 F 5 )] 3 (1 b), Al[OC(CF 3 ) 3 ] 4 (1 c)) was replaced by white phosphorus (P 4 ) or yellow arsenic (As 4 ) to yield [(DPFN)Cu 2 (μ,η 2 : η 2 -E 4 )][X] 2 (E=P (2 a-c), As (3 a-c)). The molecular structures in the solid state reveal novel coordination modes for E 4 tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E 4 tetrahedra. Reactions with N-heterocyclic carbenes (NHCs) led to replacement of the E 4 tetrahedra with release of P 4 or As 4 and formation of [(DPFN)Cu 2 (μ,η 1 : η 1 - Me NHC)][X] 2 (4 a,b) or to an opening of one E-E bond leading to an unusual E 4 butterfly structural motif in [(DPFN)Cu 2 (μ,η 1 : η 1 -E 4 Dipp NHC)][X] 2 (E=P (5 a,b), E=As (6)). With a cyclic alkyl amino carbene ( Et CAAC), cleavage of two As-As bonds was observed to give two isomers of [(DPFN)Cu 2 (μ,η 2 : η 2 -As 4 Et CAAC)][X] 2 (7 a,b) with an unusual As 4 -triangle+1 unit.

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

Excited State Dynamics of a Conformationally Fluxional Copper Coordination Complex

The conversion of solar energy into chemical fuel represents a capstone goal of the 21st century and has the potential to supply terawatts of power in a globally distributed manner. However, the disparate time scales of photodriven charge separation (~fs) and steps in chemical reactions (~μs) represent an inherent bottleneck in solar-to-fuels technology. Here to address this discrepancy, we are developing earth-abundant coordination complexes that undergo light-induced conformational rearrangements such that charge separation (CS) is hastened, while charge recombination (CR) is slowed. To these ends, we report the preparation and characterization of a new series of conformationally fluxional copper coordination complexes that contain a twisted intramolecular charge transfer (TICT) fluorophore as part of their ligand scaffold. Structural and spectroscopic characterization of the Cu(I) and Cu(II) complexes formed with these ligands in their ground states establish oxidation state-dependent conformational dynamicity, while time-resolved emission and transient absorption spectroscopies define the photopysical parameters of photo-induced excited states. Building on initial reports with a related set of molecules, the improved ligand design presented here greatly simplifies the observed photophysics, effectively shutting down unwanted ligand-centered excited states previously observed. Finally, time-dependent density functional theory (TDDFT) analyses reveal an unusual metal-to-TICT electronic transition only reported once before, and though the formation of a CS state is not observed directly through experiments, TDDFT geometry optimizations in the excited states support the formation of transient Cu(II) CS species, lending credence to the potential success of our approach. These studies establish a clear model for the excited state dynamics at play in proof-of-concept systems and clarify key design parameters for future optimizations toward achieving long-lived CS via photoinduced conformational gating.

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

Improved Performance of Cu(InGa)(SeS) 2 PV Modules Using the Reaction of Metal Precursors. Final Report

This project “Improved Performance of Cu(InGa)(SeS) 2 PV Modules using the Reaction of Metal Precursors” was a partnership led by the Institute of Energy Conversion (IEC) at the University of Delaware with Columbia University and the Molecular Foundry at the Lawrence Berkeley National Laboratory. The aim was to develop pathways to improve Cu(InGa)(SeS) 2 (CIGSS) thin film photovoltaic modules using processes compatible with low manufacturing cost. The CIGSS approach investigated was a two-step process including deposition of metal precursor films following by reaction in hydride gases utilizing IEC’s novel reactor. The process was similar to that under commercial development by the project’s industry partner Stion. When Stion went out of business mid-project the focus changed to a rapid thermal process considered more commercially viable. Approaches to improve the performance of solar cells using the reacted films focused on two material innovations. First, the overall Ga content was increased to increase the operating voltage, which is desirable for scale-up to commercial modules. Second, the processing and performance advantages arising from Ag alloying were investigated. Advanced characterization guided process and material development including control of relative composition gradients. Research on the formation of Cu-Ga-In metal precursors utilized sputtering deposition which is normally used in commercial applications. The work resulted in processes for deposition of precursor stacks with increased relative Ga content and effects of deposition parameters on morphology and phase composition were established. It was shown that the metal precursor films have comparable phase composition and morphology so subsequent reaction follows from the same starting point. The addition of Ag to the metal precursors gave more uniform morphology and improved adhesion of reacted films which enable higher reaction temperature for faster processing. A novel outcome was the discovery of a previously undocumented material phase in sputter-deposited and evaporated Ag-Cu-In-Ga thin films. Hydride gas reaction processes including time-temperature-concentration profiles were developed for different precursor compositions. This enables control of composition profiles to engineer through-film gradients for solar cell optimization with characterization and simulations used to correlate measured film composition profiles to measurements of devices. In particular, the gradient of sulfur at the front of the CIGSS film was found to be critical. The simulations guided process development leading to improved reproducibility of devices improved performance with higher Ga content and higher voltage. With Ag-alloyed precursors, the reaction pathways leading were determined. A significant finding was that Ag-alloying increases the reaction rate to completely convert precursor films to the final chalcopyrite which could enable reduced reaction time to benefit manufacturability. To maintain potential commercial viability, the process under investigation was refocused to a rapid thermal process that could potentially be incorporated into an in-line process for manufacturing. Precursors with different composition were capped with an extra selenium layer and reacted in hydrogen sulfide 5-15 minutes, compared to typically 2 hours in the previous multi-step batch process. Critical RTP parameters were identified to control the reaction. Further optimization would be needed for high efficiency solar cells but pathways to high quality devices with further optimization and improved heating uniformity were developed. The project also developed new optoelectronic characterization approaches with a focus on development and application of spatial- and time-resolved photoluminescence and a custom mapping photoluminescence microscope built. It was shown how critical electronic transport properties strongly depend on the chemical composition of the material and that a wide range of samples show inhomogeneity on a length scale larger than the grains in the films. Additionally, two-photon excitation capability was developed to distinguish bulk vs surface losses. The project advances the state-of-the -art for precursor reaction processes in several ways that could impact manufacturing. This includes validation of approaches to increase voltage and establishment of model-guided control to form optimal composition profiles. The application of process control approaches with knowledge of phase formation and reaction pathways can be critically valuable in designing a large-scale process.

14 SOLAR ENERGY↗
DOE OSTI2022

Dynamical Change of Valence States and Structure in NiCu 3 Nanoparticles during Redox Cycling

Alloyed materials are promising candidates to improve catalytic processes. Ni–Cu nanoparticles are used for various reactions, including processes with biomass-derived components. However, dynamical restructuring effects alter the catalytic properties and can deactivate the sample. To understand these structural modifications, a multimodal investigation of NiCu 3 /C was performed to determine compositional and morphological changes during a redox cycle to simulate reduction and oxidation of the catalyst during reaction. We exploit a novel correlative, multimodal approach that combines in situ X-ray absorption spectroscopy (XAS) and in situ scanning transmission electron microscopy and electron energy-loss spectroscopy (STEM-EELS) to describe changes that occur in the sample in realistic conditions. In the fresh sample, there are two morphologies present: core–shell and hollow. Segregation of Cu was observed in both types of particles after synthesis, with Cu being more oxidized in the hollow structures. Upon reduction for 2 h under H 2 at 400 °C, the Cu was reduced, although segregation of Cu and Ni was still observed. Subsequent exposure to O 2 at 400 °C led to a strong reoxidation of Cu with the formation of hollow particles with compositional heterogeneities. The oxidation of metals and segregation phenomena can be related to known catalytic properties of NiCu 3 /C particles, especially regarding the hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Ab initio molecular dynamics free energy study of enhanced copper (II) dimerization on mineral surfaces

Understanding the adsorption of isolated metal cations from water on to mineral surfaces is critical for toxic waste retention and cleanup in the environment. Heterogeneous nucleation of metal oxyhydroxides and other minerals on material surfaces is key to crystal growth and dissolution. The link connecting these two areas, namely cation dimerization and polymerization, is far less understood. In this work we apply ab initio molecular dynamics calculations to examine the coordination structure of hydroxide-bridged Cu(II) dimers, and the free energy changes associated with Cu(II) dimerization on silica surfaces. The dimer dissociation pathway involves sequential breaking of two Cu 2+ -OH – bonds, yielding three local minima in the free energy profiles associated with 0-2 OH – bridges between the metal cations, and requires the design of a (to our knowledge) novel reaction coordinate for the simulations. Cu(II) adsorbed on silica surfaces are found to exhibit stronger tendency towards dimerization than when residing in water. Cluster-plus-implicit-solvent methods yield incorrect trends if OH – hydration is not correctly depicted. The predicted free energy landscapes are consistent with fast equilibrium times (seconds) among adsorbed structures, and favor Cu 2+ dimer formation on silica surfaces over monomer adsorption.

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

Dynamic response of 17-4 stainless steel as a function of manufacturing method and heat treatment

We present a series of plate-impact experiments on 17-4 stainless steel to study the effect of manufacturing method and heat treatment on the Hugoniot elastic limit (HEL), Hugoniot, phase transformation stress, and spallation strength. Two traditional manufacturing methods were considered, wrought processing and casting, as well as two additive manufacturing methods, laser powder-bed fusion (LPBF) and wire-fed electron beam (EBAM). For both LPBF and EBAM 17-4 stainless steel variants, two billets were printed, enabling the application of two unique heat treatments. The HEL stress depended heavily on the thermal history, with the HEL increasing after the formation of Cu-rich precipitates via heat treatment. The Hugoniot response both below and above the phase transition was unaffected by the manufacturing method or heat treatment. The phase transition stress depended heavily on the thermal history, with its variation being attributed to the presence of various microstructural features. This is supported by a marked increase in the phase transition stress after precipitation hardening. These results suggest that the notion of the phase transition stress being dictated by bulk composition is an oversimplification and the stress fields generated by the meso-scale structure are a dominant force. The spallation strength was lower in the cast material compared to all other 17-4 stainless steel variants due to the presence of brittle δ-ferrite inclusions. Additionally, a drop in the tensile strain-rate was observed in the spallation response above the phase transition stress, which was hypothesized to stem from the kinetics of the reversion to the low-pressure phase during spall.

Compressive stress↗
DOE OSTI2020

Atomic-Scale Dynamic Interaction of H 2 O Molecules with Cu Surface

Atomic-scale interaction of water vapor with metal surfaces beyond surface adsorption under technologically relevant conditions remains mostly unexplored. Using aberration-corrected environmental transmission electron microscopy, we reveal the dynamic surface activation of Cu by H 2 O at elevated temperature and pressure. In this study, we find a structural transition from flat to corrugated surface for the Cu(011) under low water-vapor pressure. Increasing the water-vapor pressure leads to the surface reaction of Cu with dissociated H 2 O, resulting in the formation of a metastable “bilayer” Cu-O-H phase. Corroborated by density functional theory and ab initio molecular dynamics calculations, the cooperative O and OH interaction with Cu is responsible for the formation and subsurface propagation of this phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Carrier Mobility Modulation in Cu 2 Se Composites Using Coherent Cu 4 TiSe 4 Inclusions Leads to Enhanced Thermoelectric Performance

Carrier transport engineering in bulk semiconductors using inclusion phases often results in the deterioration of carrier mobility (μ) owing to enhanced carrier scattering at phase boundaries. Here, we show by leveraging the temperature-induced structural transition between the α-Cu 2 Se and β-Cu 2 Se polymorphs that the incorporation of Cu 4 TiSe 4 inclusions within the Cu 2 Se matrix results in a gradual large drop in the carrier mobility at temperatures below 400 K (α-Cu 2 Se), whereas the carrier mobility remains unchanged at higher temperatures, where the β-Cu 2 Se polymorph dominates. The sharp discrepancy in the electronic transport within the α-Cu 2 Se and β-Cu 2 Se matrices is associated with the formation of incoherent α-Cu 2 Se/Cu 4 TiSe 4 interfaces, owing to the difference in their atomic structures and lattice parameters, which results in enhanced carrier scattering. In contrast, the similarity of the Se sublattices between β-Cu 2 Se and Cu 4 TiSe 4 gives rise to coherent phase boundaries and good band alignment, which promote carrier transport across the interfaces. Interestingly, the different cation arrangements in Cu 4 TiSe 4 and β-Cu 2 Se contribute to enhanced phonon scattering at the interfaces, which leads to a reduction in the lattice thermal conductivity. The large reduction in the total thermal conductivity while preserving the high power factor of β-Cu 2 Se in the (1–x)Cu 2 Se/(x)Cu 4 TiSe 4 composites results in an improved ZT of 1.2 at 850 K, with an average ZT of 0.84 (500–850 K) for the composite with x = 0.01. Furthermore, this work highlights the importance of structural similarity between the matrix and inclusions when designing thermoelectric materials with improved energy conversion efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2025

An impermeable copper surface monolayer with high-temperature oxidation resistance

Despite numerous efforts involving surface coating, doping, and alloying, maintaining surface stability of metal at high temperatures without compromising intrinsic properties has remained challenging. Here, we present a pragmatic method to address the accelerated oxidation of Cu, Ni, and Fe at temperatures exceeding 200 °C. Inspired by the concept that oxygen (O) itself can effectively obstruct the pathway of O infiltration, this study proposes the immobilization of O on the metal surface. Through extensive calculations considering various elements (C, Al, Si, Ge, Ga, In, and Sn) to anchor O on Cu surfaces, Si emerges as the optimal element. The theoretical findings are validated through systematic sputtering deposition experiments. The introduction of anchoring elements to reinforce Cu–O bonds enables the formation of an atomically thin barrier on the Cu surface, rendering it impermeable to O even at high temperatures (400 °C) while preserving its intrinsic conductivity. This oxidation resistance, facilitated by the impermeable atomic monolayer, opens promising opportunities for researchers and industries to overcome limitations associated with the use of oxidizable metal films.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Low-temperature liquid-phase formation of environmentally stable copper halide nanocrystal superlattices and their application to anticounterfeiting patterns

Nanocrystal superlattices have the potential to create a new class of semiconductor materials by combining the photophysical properties of individual nanocrystals with bulk-like structure performance. However, the principles underlying the direct formation of superlattices in liquid phase have not been thoroughly investigated, particularly, those consisting of exciton self-trapping metal halides. Here, in this work, we explore the formation of Cs 3 Cu 2 Br 5 nanocrystal superlattices via liquid-phase crystallization of growing nanocrystals over a reaction period of only a few seconds. Importantly, the reaction temperature and the precursor concentration were found to be key parameters governing the concomitant nanocrystal growth and superlattice formation. The resulting Cs 3 Cu 2 Br 5 superlattices had a well-defined face-centered cubic structure and emitted a single-band bright blue emission when exposed to 280 nm light. Owing to their advantages, such as low toxicity, reabsorption-free, narrow absorption, strong emission, and high environmental stability, the Cs 3 Cu 2 Br 5 superlattices were applicable to anti-counterfeiting applications. Our findings shed light on the liquid-phase assembly of nanocrystals into superlattices and highlight the potential applications of the superlattices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗