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At least 973 records · Page 54

Vertically oriented arrays of ReS 2 nanosheets for electrochemical energy storage and electrocatalysis

Here, transition-metal dichalcogenide (TMD) nanolayers show potential as high-performance catalysts in energy conversion and storage devices. Synthetic TMDs produced by chemical-vapor deposition (CVD) methods tend to grow parallel to the growth substrate. Here, we show that with the right precursors and appropriate tuning of the CVD growth conditions, ReS 2 nanosheets can be made to orient perpendicular to the growth substrate. This accomplishes two important objectives; first, it drastically increases the wetted or exposed surface area of the ReS 2 sheets, and second, it exposes the sharp edges and corners of the ReS 2 sheets. We show that these structural features of the vertically grown ReS 2 sheets can be exploited to significantly improve their performance as polysulfide immobilizers and electrochemical catalysts in lithium–sulfur (Li–S) batteries and in hydrogen evolution reactions (HER). After 300 cycles, the specific capacity of the Li–S battery with vertical ReS 2 catalyst is retained above 750 mA h g –1 , with only ~0.063% capacity decay per cycle, much better than the baseline battery (without ReS 2 ), which shows ~0.184% capacity decay per cycle under the same test conditions. As a HER catalyst, the vertical ReS 2 provides very small onset overpotential (<100 mV) and an exceptional exchange-current density (~67.6 μA/cm 2 ), which is vastly superior to the baseline electrode without ReS 2 .

2D materials↗

Electrochemical and Chemical Reactivities of Titanium Oxide-Based Materials with a Chloroaluminate Ionic Liquid Electrolyte for Aluminum Batteries

Here, by selecting three different types of electrode materials, we intended to better understand the Al 3+ intercalation chemistry of titanium oxide-based frameworks with an acidic chloroaluminate electrolyte. In agreement with previous reports, we confirmed that the native interstitial sites of anatase TiO 2 are less prone to accommodate Al 3 + than Li + or Na + ions, while introducing cationic vacancies largely increases the electrochemical storage capacity. Upon the first cycle, the highest reversible capacity, up to 277 mAh/g, was obtained for a hydrated layered structure featuring cationic vacancies. Total scattering data showed that the insertion of Al 3+ ions induced a strong distortion of the framework. In addition, combined 27 Al MAS NMR and DFT calculations revealed that in oxy-hydroxylated vacant sites, the coordination mode of Al 3+ ions depends on the arrangement of anions around vacancies inducing the occurrence of 4-, 5-, and 6-fold coordination modes. Further cycling experiments revealed a progressive capacity fading for all electrode materials. Using cyclic voltammetry on the used electrolyte, we evidenced that a partial dissolution has occurred, which is more pronounced for the layered hydrate compound, and that solubilized species are electrochemically active, giving rise to specific signatures in both CVs and galvanostatic experiments. Raman spectroscopy enabled us to characterize these species, which are derived from the Ti-Cl system. The solubilized species, however, eventually precipitated, as shown by a purple deposit observed on the separator and tentatively assigned to TiCl 3 , known to be insoluble in this medium. By providing further information on the Al 3+ intercalation chemistry and a better understanding of the electrochemical and chemical reactivities of electrode materials, this work will enable progress to be made in the development of aluminum-ion batteries.

Al3+-ion insertion chemistry↗

Reversible Interlayer Sliding and Conductivity Changes in Adaptive Tetrathiafulvalene-Based Covalent Organic Frameworks

Ordered interlayer stacking is intrinsic in two-dimensional covalent organic frameworks (2D COFs) and has strong implications on COF's optoelectronic properties. Reversible interlayer sliding, corresponding to shearing of 2D layers along their basal plane, is an appealing dynamic control of both structures and properties, yet it remains unexplored in the 2D COF field. In this paper, we demonstrate that the reversible interlayer sliding can be realized in an imine-linked tetrathiafulvalene (TTF)-based COF TTF-DMTA. The solvent treatment induces crystalline phase changes between the proposed staircase-like sql net structure and a slightly slipped eclipsed sql net structure. The solvation-induced crystallinity changes correlate well with reversible spectroscopic and electrical conductivity changes as demonstrated in oriented COF thin films. In contrast, no reversible switching is observed in a related TTF-TA COF, which differs from TTF-DMTA in terms of the absence of methoxy groups on the phenylene linkers. This work represents the first 2D COF example of which eclipsed and staircase-like aggregated states are interchangeably accessed via interlayer sliding, an uncharted structural feature that may enable applications such as chemiresistive sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Growth and Performance of High-Quality SWCNT Forests on Inconel Foils as Lithium-Ion Battery Anodes

Large-scale production of vertically aligned single-walled carbon nanotubes (VA-SWCNTs) on metal foils promises to enable technological advancements in many fields, from functional composites to energy storage to thermal interfaces. In this work, we demonstrate growth of high-quality (G/D > 6, average diameters ~ 2–3 nm, densities > 10 12 cm –2 ) VA-SWCNTs on Inconel metal for use as a lithium-ion battery (LIB) anode. Scale-up of SWCNT growth on Inconel 625 to 100 cm 2 exhibits nearly invariant CNT structural properties, even when synthesis is performed near atmospheric pressure, and this robustness is attributed to a growth kinetic regime dominated by the carbon precursor diffusion in the bulk gas mixture. SWCNT forests produced on large-area metal substrates at close to atmospheric pressure possess a combination of structural features that are among the best demonstrated so far in the literature for growth on metal foils. Leveraging these achievements for energy applications, we demonstrate a VA-SWCNT LIB anode with capacity >1200 mAh/g at 1.0C and stable cycling beyond 300 cycles. Furthermore, this robust synthesis of high-quality VA-SWCNTs on metal foils presents a promising route toward mass production of high-performance CNT devices for a broad range of applications.

Energy↗

Phase-field based Multiscale Modeling of Heterogeneous Solid Electrolytes: Applications to Nanoporous Li 3 PS 4

Modeling the effective ion conductivities of heterogeneous solid electrolytes typically involves the use of a computer-generated microstructure consisting of randomly or uniformly oriented fillers in a matrix. But, the structural features of the filler/matrix interface, which critically determine the interface ion conductivity and the microstructure morphology, have not been considered during the microstructure generation. In using nanoporous β-Li 3 PS 4 electrolyte as an example, we develop a phase-field model that enables generating nanoporous microstructures of different porosities and connectivity patterns based on the depth and the energy of the surface (pore/electrolyte interface), both of which are predicted through density functional theory (DFT) calculations. Room-temperature effective ion conductivities of the generated microstructures are then calculated numerically, using DFT-estimated surface Li-ion conductivity (3.14×10 -3 S/cm) and experimentally measured bulk Li-ion conductivity (8.93×10 -7 S/cm) of β-Li 3 PS 4 as the inputs. We also use the generated microstructures to inform effective medium theories to rapidly predict the effective ion conductivity via analytical calculations. Furthemore, when porosity approaches the percolation threshold, both the numerical and analytical methods predict a significantly enhanced Li-ion conductivity (1.74×10 -4 S/cm) that is in good agreement with experimental data (1.64×10 -4 S/cm). The present phase-field based multiscale model is generally applicable to predict both the microstructure patterns and the effective properties of heterogeneous solid electrolytes.

36 MATERIALS SCIENCE↗

Three-Dimensional Graphene–Carbon Nanotube–Ni Hierarchical Architecture as a Polysulfide Trap for Lithium–Sulfur Batteries

We report that despite their high energy density and affordable cost compared to lithium-ion (Li-ion) batteries, lithium-sulfur (Li-S) batteries still endure from slow reaction kinetics and capacity loss induced by the insulating sulfur and severe polysulfide diffusion. To address these issues, we report here nickel nanoparticles filled in vertically grown carbon nanotubes on graphene sheets (graphene-carbon nanotube-nickel composite (Gr-CNT-Ni)) that are coated onto a polypropylene separator as a polysulfide trap for the construction of high-loading sulfur cathodes. The hierarchical porous framework of Gr-CNT physically entraps and immobilizes the active material sulfur, while the strong chemical interaction with Ni nanoparticles in Gr-CNT-Ni inhibits polysulfide diffusion. The covalently interconnected electron conduction channels and carbon shell-confined metal active sites provide feasible paths for the continual regeneration of active material during the charge/discharge process. Benefitting from these novel morphological and structural features, the Li-S cell with the Gr-CNT-Ni as a polysulfide trap demonstrates high specific capacity and good cycle life. Lastly, this work provides new avenues for synergistically combining the advantages of hierarchical porous carbon architectures and metal active sites for the development of high-performance cathodes for Li-S batteries.

25 ENERGY STORAGE↗

Expanding Interlayer Spacing of Hard Carbon by Natural K + Doping to Boost Na-Ion Storage

Heteroatom-doped carbon is an attractive material for anodes in lithium/sodium ion batteries as a replacement for the traditional graphite anodes. However, the complex fabrication process and high-cost force these carbon materials far from the practical applications. Here we report a low-cost, natural potassium-doped carbon material, which is directly carbonized from the coconut endocarp – a kind of the high-potassium contained biomass materials. The obtained carbon structure features an expanded d(002)-spacing (0.4 nm) originating from the super-high potassium content (6654 mg kg-1). Because of the improvement on charge transfer kinetics and electrical properties, the potassium-doped carbon anode exhibits promising electrochemical performance in sodium ion batteries, including high initial reversible capacity (314 mAh g-1) and good cycle stability (289 mAh g-1 after 200 cycles). Additionally, this work opens up a new approach for the design of heteroatom-doped carbon materials from the view of the natural environmental friendly.

Wu, Feng↗

Highly Stable Luminous “Snakes” from CsPbX 3 Perovskite Nanocrystals Anchored on Amine-Coated Silica Nanowires

CsPbX 3 (X = Cl, Br, and I) perovskite nanocrystals (NCs) are known for their exceptional optoelectronic properties, yet the material's instability toward polar solvents, heat, or UV irradiation greatly limits its further applications. Herein, an efficient in situ growing strategy has been developed to give highly stable perovskite NC composites (abbreviated CsPbX 3 @CA-SiO 2 ) by anchoring CsPbX 3 NCs onto silica nanowires (NWs), which effectively depresses the optical degradation of their photoluminescence (PL) and enhances stability. The preparation of surface-functionalized serpentine silica NWs is realized by a sol-gel process involving hydrolysis of a mixture of tetraethyl orthosilicate (TEOS), 3-aminopropyltriethoxysilane (APTES), and trimethoxy(octadecyl)silane (TMODS) in a water/oil emulsion. The serpentine NWs are formed via an anisotropic growth with lengths up to 8 μm. The free amino groups are employed as surface ligands for growing perovskite NCs, yielding distributed monodisperse NCs (~8 nm) around the NW matrix. The emission wavelength is tunable by simple variation of the halide compositions (CsPbX 3 , X = Cl, Br, or I), and the composites demonstrate a high photoluminescence quantum yield (PLQY 32-69%). Additionally, we have demonstrated the composites CsPbX 3 @CA-SiO 2 can be self-woven to form a porous 3D hierarchical NWs membrane, giving rise to a superhydrophobic surface with hierarchical micro/nano structural features. The resulting composites exhibit high stability toward water, heat, and UV irradiation. Finally, this work elucidates an effective strategy to incorporate perovskite nanocrystals onto functional matrices as multifunctional stable light sources.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Highly Ordered Mesoporous Bimetallic Phosphides as Efficient Oxygen Evolution Electrocatalysts

Oxygen evolution from water using earth abundant transition metal based catalysts is of importance for the commercialization of water electrolyzer. Herein, we report a novel hard templating method to synthesize transition metal phosphides with uniform shape and size. By virtue of the structural feature, synergistic effect among metals and the in situ formed active species, the as-prepared phosphides with optimized composition present enhanced electrocatalytic performance towards oxygen evolution reaction in alkaline solution. In details, the most efficient catalyst reaches a current density of 10 mA/cm2 at a potential of 1.511 V vs reversible hydrogen electrode, which is much lower than that of commercial RuO2 catalyst. Our work offers a new strategy to optimize the catalysts for water splitting by controlling the morphology and composition.

Environmental Molecular Sciences Laboratory↗

Molecular Dynamics Investigation of the Relaxation Mechanism of Entangled Polymers after a Large Step Deformation

The chain retraction hypothesis of the tube model for nonlinear polymer rheology has been challenged by the recent small-angle neutron scattering (SANS) experiment. In this study, we further examine the microscopic relaxation mechanism of entangled polymer melts after a large step uniaxial extension by using large-scale molecular dynamics simulation. We show that the unique structural features associated with the chain retraction mechanism of the tube model are absent in our simulations, in agreement with the previous experimental results. In contrast to SANS experiments, molecular dynamics simulations allow us to accurately and unambiguously determine the evolution of the radius of gyration tensor of a long polymer chain after a large step deformation. Contrary to the prediction of the tube model, our simulations reveal that the radius of gyration in the perpendicular direction to stretching increases monotonically toward its equilibrium value throughout the stress relaxation. These results provide a critical step in improving our understanding of nonlinear rheology of entangled polymers.

36 MATERIALS SCIENCE↗

High-Resolution Full-Field Structural Microscopy of the Voltage-Induced Filament Formation in VO 2 -Based Neuromorphic Devices

In order to make neuromorphic functions in memristive devices more efficient, information about the structural properties of filament formation at the micro- and mesoscopic scales is necessary. Despite extensive research on VO 2 , a key material due to its filament formation, local operando structural measurements remain challenging and often involve destructive specimen preparation and long rastering times, greatly limiting the scope of experimental studies. Utilizing dark-field X-ray microscopy (DFXM), a fullfield imaging modality, structural signatures of the filament formation process operando are revealed in VO 2 devices. DFXM experiments illustrate that rutile filaments contain isolated monoclinic clusters, indicating structural nonuniformity interior to the filament. The formation of the rutile phase beneath device electrodes was shown to precede filament development, followed by the formation of filament paths guided by nucleation sites within the device. Finally, a medium-term (<30 min) memory mechanism is observed in VO 2 , mediated by sites within the device gap that tend to switch at significantly lower voltages after electrical cycling, a tendency that persists through a brief thermal reset. High spatial resolution, large field-of-view, structure selectivity, and fast signal acquisition of DFXM provided insight into structural features of the filamentary channel and surrounding regions during voltage cycling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

One-Dimensional Electron Gas Confined along Nanowrinkles in a Unidirectional Charge Density Wave Material

Two-dimensional (2D) materials inherently exhibit instabilities. Structurally, this may lead to modulations along the third dimension, e.g., wrinkles. Electronically, 2D instabilities can manifest themselves as charge density waves (CDWs). Although wrinkles can alter anisotropic electronic structures susceptible to forming CDWs, less is known about their impact on broken-symmetry ground states. Here, in this study, using scanning tunneling microscopy and spectroscopy, we investigate the CDW states on the wrinkled surface of DyTe 3 . We identify elongated, parallel nanoscale wrinkles stabilized by ribbon-shaped defects. Interestingly, the CDW order persists across the nanowrinkles with a gradual phase shift but is locally suppressed near the defects, where phase windings occur. In addition, these defects induce quantum confinement effects along the nanowrinkles, indicating the presence of one-dimensional metallic states with hole- like dispersion, while angle-resolved photoemission spectroscopy identifies a gap along the wrinkle direction. We ascribe this discrepancy to strain-induced changes in the Fermi surface, which lead to the closure of the gap at the sites of the nanowrinkles. Taken together, our results underscore the complex interplay between structural features and Fermi surface topology, allowing for the deliberate manipulation of quantum states in strongly correlated systems via local crystal deformations.

nanowrinkles↗

Fast Fractionation of Technical Lignins by Organic Cosolvents

A simple and fast fractionation method was developed to obtain carbohydrate-free lignin with well-defined characteristics, such as narrowly distributed molecular weights and a tunable chemical structure for specific applications. In this study, an industrial softwood kraft lignin and a hardwood CELF lignin (coproduct lignin obtained from cosolvent enhanced lignocellulosic fractionation pretreatment) were dissolved in acetone–methanol and tetrahydrofuran–methanol cosolvents, respectively. Hexane was applied as the antisolvent for sequential precipitation of both lignin preparations. A thorough characterization including various NMR techniques (31P, quantitative 13C, and 2D-HSQC), GPC, DSC and TGA was conducted to correlate the molecular weight of obtained lignin fractions with their structural features including distributions of aliphatic and phenolic hydroxyl groups and relative abundance of interunit linkages. It was found that approximately 10% of the softwood kraft lignin was lignin carbohydrate complexes, and the latter one could be removed efficiently by decreasing polarity of the cosolvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Protein Structure on Iron–Polypeptide Vibrational Dynamic Coupling in Cytochrome c

Cytochrome c (Cyt c) has a heme covalently bound to the polypeptide via a Cys-X-X-Cys-His (CXXCH) linker that is located in the interface region for protein–protein interactions. To determine whether the polypeptide matrix influences iron vibrational dynamics, nuclear resonance vibrational spectroscopy (NRVS) measurements were performed on 57 Fe-labeled ferric Hydrogenobacter thermophilus cytochrome c-552, and variants M13V, M13V/K22M, and A7F, which have structural modifications that alter the composition or environment of the CXXCH pentapeptide loop. Simulations of the NRVS data indicate that the 150–325 cm –1 region is dominated by N His –Fe–S Met axial ligand and polypeptide motions, while the 325–400 cm –1 region shows dominant contributions from ν(Fe–N Pyr ) (Pyr = pyrrole) and other heme-based modes. Diagnostic spectral signatures that directly relate to structural features of the heme active site are identified using a quantum chemistry-centered normal coordinate analysis (QCC-NCA). In particular, spectral features that directly correlate with CXXCH loop stiffness, the strength of the Fe–His interaction, and the degree of heme distortion are identified. Cumulative results from our investigation suggest that compared to the wild type (wt), variants M13V and M13V/K22M have a more rigid CXXCH pentapeptide segment, a stronger Fe–N His interaction, and a more ruffled heme. Conversely, the A7F variant has a more planar heme and a weaker Fe–NHis bond. These results are correlated to the observed changes in reduction potential between wt protein and the variants studied here. Lastly, we discuss the implications of these results for Cyt c biogenesis and electron transfer.

59 BASIC BIOLOGICAL SCIENCES↗

Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2

Our central premise is that catalytic scientists can learn by studying how these important metabolic processes occur in nature. Complementarily, biochemists can learn by studying how catalytic scientists view these same chemical transformations promoted by synthetic catalysts. From these studies, hypotheses can be developed and tested through manipulation of enzyme structure and by synthesizing simple molecular catalysts to incorporate different structural features of the enzymes. It is hoped that these studies will lead to new and useful concepts in catalyst design for fuel production and utilization. This paper describes the results of a workshop held to explore these concepts in regard to the development of new and more efficient catalytic processes for the conversion of CO2 to a variety of carbon-based fuels. The organization of this overview/review is as follows: 1) The first section briefly explores how interactions between the catalysis and biological communities have been fruitful in developing new catalysts for the reduction of protons to hydrogen, the simplest fuel generation reaction. 2) The second section assesses the state of the art in both biological and chemical reduction of CO2 by two electrons to form either carbon monoxide (CO) or formate (HCOO-). It also attempts to identify common principles between biological and synthetic catalysts and productive areas for future research. 3) The third section explores both biological and chemical processes that result in the reduction of CO2 beyond the level of CO and formate, again seeking to identify common principles and productive areas of future research. 4) The fourth section explores the formation of carbon-carbon bonds in biological and chemical systems in the same vein as the other sections. 5) A fifth section addresses the role of non-redox reactions of CO2 in biological systems and their role in carbon metabolism, with a parallel discussion of chemical systems. 6) In section 6, the topics of electrode modification, photochemical systems, and tandem catalysis are briefly discussed. These areas may be important for developing practical systems for CO2 reduction, and they share the common theme of coupling chemical reactions. 7) Section 7 describes some of the crosscutting activities that are critical for advancing the science underpinning catalyst development. 8) The last section attempts to summarize common issues in biological and chemical catalysis and to identify challenges that must be addressed to achieve practical catalysts that are suitable for the reduction of CO2 to fuels.

Environmental Molecular Sciences Laboratory↗

Two-Dimensional Mineral [Pb 2 BiS 3 ][AuTe 2 ]: High-Mobility Charge Carriers in Single-Atom-Thick Layers

Two-dimensional (2D) electronic systems are of wide interest due to their richness in chemical and physical phenomena and potential for technological applications. Here we report that [Pb2BiS3][AuTe2], known as the naturally occurring mineral buckhornite, hosts 2D carriers in single-atom-thick layers. The structure is composed of stacking layers of weakly coupled [Pb2BiS3] and [AuTe2] sheets. The insulating [Pb2BiS3] sheet inhibits interlayer charge hopping and confines the carriers in the basal plane of the single-atom-thick [AuTe2] layer. Magneto-transport measurements on synthesized samples and theoretical calculations show that [Pb2BiS3][AuTe2] is a multiband semimetal with a compensated density of electrons and holes, which exhibits a high hole carrier mobility of similar to 1360 cm(2)/(V s). This material possesses an extremely large anisotropy, G = rho(c)/rho(ab) approximate to 10(4), comparable to those of the benchmark 2D materials graphite and Bi2Sr2CaCu2O6+delta. The electronic structure features linear band dispersion at the Fermi level and ultrahigh Fermi velocities of 10(6) m/s, which are virtually identical to those of graphene. The weak interlayer coupling gives rise to the highly cleavable property of the single crystal specimens. Our results provide a novel candidate for a monolayer platform to investigate emerging electronic properties.

Fang, Lei↗

Local Chemical Clustering Enabled Ultrahigh Capacitive Energy Storage in Pb-Free Relaxors

Designing Pb-free relaxors with both a high capacitive energy density (W rec ) and high storage efficiency (η) remains a remarkable challenge for cutting-edge pulsed power technologies. Local compositional heterogeneity is crucial for achieving complex polar structure in solid solution relaxors, but its role in optimizing energy storage properties is often overlooked. Here, in this paper, we report that an exceptionally high W rec of 15.2 J cm –3 along with an ultrahigh η of 91% can be achieved through designing local chemical clustering in Bi 0.5 Na 0.5 TiO 3 –BaTiO 3 -based relaxors. A three-dimensional atomistic model derived from neutron/X-ray total scattering combined with reverse Monte Carlo method reveals the presence of subnanometer scale clustering of Bi, Na, and Ba, which host differentiated polar displacements, and confirming the prediction by density functional theory calculations. This leads to a polar state with small polar clusters and strong length and direction fluctuations in unit-cell polar vectors, thus manifesting improved high-field polarizability, steadily reduced hysteresis, and high breakdown strength macroscopically. The favorable polar structure features also result in a unique field-increased η, excellent stability, and superior discharge capacity. Our work demonstrates that the hidden local chemical order exerts a significant impact on the polarization characteristic of relaxors, and can be exploited for accessing superior energy storage performance.

25 ENERGY STORAGE↗

Sterically Encumbered Aryl Isocyanides Extend Excited-State Lifetimes and Improve the Photocatalytic Performance of Three-Coordinate Copper(I) β-Diketiminate Charge-Transfer Chromophores

Copper(I) complexes are prominent candidates to replace noble metal-based photosensitizers. We recently introduced a three-coordinate design for copper(I) charge-transfer chromophores that pair β-diketiminate ligands with aryl isocyanides. The excited-state lifetime in these compounds can be extended using a bichromophoric “triplet reservoir” strategy, which comes at the expense of a decrease in excited-state energy and reducing power. In this work, we introduce a complementary, sterically driven strategy for increasing the excited-state lifetimes of these photosensitizers, which gives a higher-energy, more strongly reducing charge-transfer triplet state than does the bichromophore approach. The compounds presented (Cu1–Cu4) have the general formula Cu(CyNacNac Me )(CN-Ar), where CyNacNac Me is a cyclohexyl-substituted β-diketiminate and CN-Ar is an aryl isocyanide with a variable steric profile. Their structural features and electrochemical and photophysical properties are described. The complexes with sterically encumbered 2,6-diisopropylphenyl or m-terphenyl isocyanide ligands (Cu2–Cu4) exhibit prolonged excited-state lifetimes relative to those of the parent 2,6-dimethylphenyl isocyanide compound Cu1. Specifically, one of the m-terphenyl isocyanide compounds, Cu3, displays an excited-state lifetime of 276 ns, approximately 30 times longer than that of Cu1 (9.3 ns). The photoluminescence quantum yield of Cu3 (0.09) also increases by two orders of magnitude compared to that of Cu1 (0.0008). Furthermore, the strong excited-state reducing power (*E ox = –2.4 V vs Fc +/0 ) and long lifetime of Cu3 lead to higher yields in photoredox and photocatalytic isomerization reactions, which include dehalogenation and/or hydrodgenation of benzophenone substrates, C–O bond activation of a lignin model substrate, and photocatalytic E/Z isomerization of stilbene.

14 SOLAR ENERGY↗