Surface-Pore-Modified N-Doped Amorphous Carbon Nanospheres Tailored with Toluene as Anode Materials for Lithium-Ion Batteries.

The surface modification of amorphous carbon nanospheres (ACNs) through templates has attracted great attention due to its great success in improving the electrochemical properties of lithium storage materials. Herein, a safe methodology with toluene as a soft template is employed to tailor the nanostructure, resulting in ACNs with tunable surface pores. Extensive characterizations through transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption isotherms elucidate the impact of surface pore modifications on the external structure, morphology, and surface area. Electrochemical assessments reveal the enhanced performance of the surface-pore-modified carbon nanospheres, particularly ACNs-100 synthesized with the addition of 100 µL toluene, in terms of the initial discharge capacity, rate performance, and cycling stability. The interesting phenomenon of persistent capacity increase is ascribed to lithium ion movement within the graphite-like interlayer, resulting in ACNs-100 experiencing a capacity upswing from an initial 320 mAh g-1 to a zenith of 655 mAh g-1 over a thousand cycles at a rate of 2 C. The findings in this study highlight the pivotal role of tailored nanostructure engineering in optimizing energy storage materials.

Non-Equilibrium Assembly of Atomically-Precise Copper Nanoclusters.

Accurate structure control in dissipative assemblies (DSAs) is vital for precise biological functions. However, accuracy and functionality of artificial DSAs are far from this objective. Herein, a novel approach is introduced by harnessing complex chemical reaction networks rooted in coordination chemistry to create atomically-precise copper nanoclusters (CuNCs), specifically Cu11(µ9-Cl)(µ3-Cl)3L6Cl (L = 4-methyl-piperazine-1-carbodithioate). Cu(I)-ligand ratio change and dynamic Cu(I)-Cu(I) metallophilic/coordination interactions enable the reorganization of CuNCs into metastable CuL2, finally converting into equilibrium [CuL·Y]Cl (Y = MeCN/H2O) via Cu(I) oxidation/reorganization and ligand exchange process. Upon adding ascorbic acid (AA), the system goes further dissipative cycles. It is observed that the encapsulated/bridging halide ions exert subtle influence on the optical properties of CuNCs and topological changes of polymeric networks when integrating CuNCs as crosslink sites. CuNCs duration/switch period could be controlled by varying the ions, AA concentration, O2 pressure and pH. Cu(I)-Cu(I) metallophilic and coordination interactions provide a versatile toolbox for designing delicate life-like materials, paving the way for DSAs with precise structures and functionalities. Furthermore, CuNCs can be employed as modular units within polymers for materials mechanics or functionalization studies.

Unveiling Carrier Relaxation Mechanism in Protonated/Deprotonated Carbon Dots and Their Solvent Effects via Ultrafast Spectroscopy.

The intricate nature of the surface structure of carbon dots (CDs) hinders a comprehensive understanding of their emission behavior. In this study, we employ two types of CDs created through acid-alkali treatments, one with surface protonation and the other with surface deprotonation, with the objective of investigating the impact of these surface modifications on carrier behavior using ultrafast spectroscopy techniques. TEM, XRD, FTIR and Raman spectra demonstrate the CDs' structure, featuring graphitic core and abundant surface functional groups. XPS confirms the successful surface modifications of CDs via protonation and deprotonation. Ultrafast transient absorption (TA) spectroscopy reveals that deprotonation modification may decelerate the relaxation process, thereby increasing the visible PL quantum yields (PLQY). Conversely, protonation may accelerate the relaxation process due to the induced low-energy absorption band, resulting in self-absorption and reduced PLQY. Furthermore, TA analysis of CDs in mixed solvents with different proportions of ethanol shows the beneficial effect of ethanol in decelerating the relaxation process, leading to an increased PLQY of 33.7 % for deprotonated CDs and 22.1 % for protonated CDs. This study illuminates the intricate relationship between surface deprotonation/protonation modifications and carrier behavior in CDs, offering a potential avenue for the design of high-brightness CDs for diverse applications.

Investigation of Excited-State Intramolecular Proton Transfer and Structural Dynamics in Bis-Benzimidazole Derivative (BBM).

The bis-benzimidazole derivative (BBM) molecule, consisting of two 2-(2'-hydroxyphenyl) benzimidazole (HBI) halves, has been synthesized and successfully utilized as a ratiometric fluorescence sensor for the sensitive detection of Cu2+ based on enol-keto excited-state intramolecular proton transfer (ESIPT). In this study, we strategically implement femtosecond stimulated Raman spectroscopy and several time-resolved electronic spectroscopies, aided by quantum chemical calculations to investigate the detailed primary photodynamics of the BBM molecule. The results demonstrate that the ESIPT from BBM-enol* to BBM-keto* was observed in only one of the HBI halves with a time constant of 300 fs; after that, the rotation of the dihedral angle between the two HBI halves generated a planarized BBM-keto* isomer in 3 ps, leading to a dynamic redshift of BBM-keto* emission.

Enhancing UV-C Photoelectron Lifetimes for Avalanche-like Photocurrents in Carbon-Doped Bi3O4Cl Nanosheets.

Interlayer electric fields in two-dimensional (2D) materials create photoelectron protecting barriers useful to mitigate electron-hole recombination. However, tuning the interlayer electric field remains challenging. Here, carbon-doped Bi3O4Cl (C:Bi3O4Cl) nanosheets are synthesized using a gas phase protocol, and n-type carriers are acquired as confirmed by the transconductance polarity of nanosheet field effect transistors. Thin C:Bi3O4Cl nanosheets show excellent 266 nm photodetector figures of merit, and an avalanche-like photocurrent is demonstrated. Decaying behaviors of photoelectrons pumped by a 266 nm laser pulse (266 nm photoelectrons) are observed using transient absorption spectroscopy, and a significant 266 nm photoelectron lifetime quality in C:Bi3O4Cl is presented. Built C:Bi3O4Cl models suggest that the interlayer electric field can be boosted by two different carbon substitutions at the inner and outer bismuth sites. This work reports a facile approach to increase the interlayer electric field in Bi3O4Cl for future UV-C photodetector applications.

Ferricyanide photo-aquation pathway revealed by combined femtosecond Kß main line and valence-to-core x-ray emission spectroscopy.

Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kß main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kß main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

Investigation of Ultrafast Configurational Photoisomerization of Bilirubin Using Femtosecond Stimulated Raman Spectroscopy.

Phototherapy is an efficient and safe way to reduce high levels of free 4Z,15Z-bilirubin (ZZ-BR) in the serum of newborns. The success of BR phototherapy lies in photoinduced configurational and structural isomerization processes that form excretable isomers. However, the physical picture of photoinduced photoisomerization of ZZ-BR is still unclear. Here, we strategically implement tunable femtosecond stimulated Raman spectroscopy and several time-resolved electronic spectroscopies, assisted by quantum chemical calculations, to dissect the detailed primary configurational isomerization dynamics of free ZZ-BR in organic solvents. The results of this study demonstrate that upon photoexcitation, ultrafast configurational isomerization proceeds by a volume-conserving "hula twist", followed by intramolecular hydrogen-bond distortion and large-scale rotation of the two dipyrrinone halves of the ZZ-BR isomer in a few picoseconds. After that, most of the population recovers back to ZZ-BR, and a very small amount is converted into stable BR isomers via structural isomerization.

Mapping the Complete Photocycle that Powers a Large Stokes Shift Red Fluorescent Protein.

Large Stokes shift (LSS) red fluorescent proteins (RFPs) are highly desirable for bioimaging advances. The RFP mKeima, with coexisting cis- and trans-isomers, holds significance as an archetypal system for LSS emission due to excited-state proton transfer (ESPT), yet the mechanisms remain elusive. We implemented femtosecond stimulated Raman spectroscopy (FSRS) and various time-resolved electronic spectroscopies, aided by quantum calculations, to dissect the cis- and trans-mKeima photocycle from ESPT, isomerization, to ground-state proton transfer in solution. This work manifests the power of FSRS with global analysis to resolve Raman fingerprints of intermediate states. Importantly, the deprotonated trans-isomer governs LSS emission at 620 nm, while the deprotonated cis-isomer's 520 nm emission is weak due to an ultrafast cis-to-trans isomerization. Complementary spectroscopic techniques as a table-top toolset are thus essential to study photochemistry in physiological environments.

Impact of Surface Trap States on Electron and Energy Transfer in CdSe Quantum Dots Studied by Femtosecond Transient Absorption Spectroscopy.

The presence of surface trap states (STSs) is one of the key factors to affect the electronic and optical properties of quantum dots (QDs), however, the exact mechanism of how STSs influence QDs remains unclear. Herein, we demonstrated the impact of STSs on electron transfer in CdSe QDs and triplet-triplet energy transfer (TTET) from CdSe to surface acceptor using femtosecond transient absorption spectroscopy. Three types of colloidal CdSe QDs, each containing various degrees of STSs as evidenced by photoluminescence and X-ray photoelectron spectroscopy, were employed. Time-resolved emission and transient absorption spectra revealed that STSs can suppress band-edge emission effectively, resulting in a remarkable decrease in the lifetime of photoelectrons in QDs from 17.1 ns to 4.9 ns. Moreover, the investigation of TTET process revealed that STSs can suppress the generation of triplet exciton and effectively inhibit band-edge emission, leading to a significant decrease in TTET from CdSe QDs to the surface acceptor. This work presented evidence for STSs influence in shaping the optoelectronic properties of QDs, making it a valuable point of reference for understanding and manipulating STSs in diverse QDs-based optoelectronic applications involving electron and energy transfer.

Deciphering Photochemical Reaction Pathways of Aqueous Tetrachloroauric Acid by X-ray Transient Absorption Spectroscopy.

Photolysis reaction pathways of [Au(III)Cl4]- in aqueous solution have been investigated by time-resolved X-ray absorption spectroscopy. Ultraviolet excitation directly breaks the Au-Cl bond in [Au(III)Cl4]- to form [Au(II)Cl3]- that becomes highly reactive within 79 ps. Disproportionation of [Au(II)Cl3]- generates [Au(I)Cl2]-, which is stable for ≤10 µs. In contrast, intense near-infrared lasers photolyze water to generate hydrated electrons, which then reduce [Au(III)Cl4]- to [Au(II)Cl3]- at 5 ns. Hydrated electrons further induce a chain reaction from [Au(II)Cl3]- to [Au(0)Cl]- by successively removing one Cl-. The zero-valency Au anions quickly polymerize and condense to form Au nanoparticles, which become the dominating product after 400 s. Our results reveal that the condensation of zero-valency Au starts with dimerization of gold clusters coordinated with chloride ions rather than direct condensation of pristine Au atoms.

Ruthenium containing molecular electrocatalyst on glassy carbon for electrochemical water splitting.

Electrochemical water splitting constitutes one of the most promising strategies for converting water into hydrogen-based fuels, and this technology is predicted to play a key role in the transition towards a carbon-neutral energy economy. To enable the design of cost-effective electrolysis cells based on this technology, new and more efficient anodes with augmented water splitting activity and stability will be required. Herein, we report an active molecular Ru-based catalyst for electrochemically-driven water oxidation (overpotential of ∼395 mV at pH 7 phosphate buffer) and two simple methods for preparing anodes by attaching this catalyst onto glassy carbon through multi-walled carbon nanotubes to improve stability as well as reactivity. The anodes modified with the molecular catalyst were characterized by a broad toolbox of microscopy and spectroscopy techniques, and interestingly no RuO2 formation was detected during electrocatalysis over 4 h. These results demonstrate that the herein presented strategy can be used to prepare anodes that rival the performance of state-of-the-art metal oxide anodes.

Large Photomultiplication by Charge-Self-Trapping for High-Response Quantum Dot Infrared Photodetectors.

PbS colloidal quantum dots (CQDs) are emerging as promising candidates for next-generation, low-cost, and high-performance infrared photodetectors. Recently, photomultiplication has been explored to improve the detectivity of CQD infrared photodetectors by doping charge-trapping material into a matrix. However, this relies on remote doping that could influence carrier transfer giving rise to limited photomultiplication. Herein, a charge-self-trapped ZnO layer is prepared by a surface reaction between acid and ZnO. Photogenerated electrons trapped by oxygen vacancy defects at the ZnO surface generate a strong interfacial electrical field and induce large photomultiplication at extremely low bias. A PbS CQD infrared photodiode based on this structure shows a response (R) of 77.0 A·W-1 and specific detectivity of 1.5 × 1011 Jones at 1550 nm under a -0.3 V bias. This self-trapped ZnO layer can be applied to other photodetectors such as perovskite-based devices.

Identification of intermediates of a molecular ruthenium catalyst for water oxidation using in situ electrochemical X-ray absorption spectroscopy.

This is the first study on a Ru(bda) (bda: 2,2'-bipyridine-6,6'-dicarboxylic acid) catalyst in solution using a home-built electrochemical cell, in combination with an energy-dispersive X-ray absorption spectroscopy setup. The oxidation state and coordination number of the catalyst during electrocatalysis could be estimated, while avoiding radiation damage from the X-rays.

Tracking Ultrafast Fluorescence Switch-On and Color-Tuned Dynamics in Acceptor-Donor-Acceptor Chromophore.

Understanding how the conformational change of conjugated molecules with acceptor-donor-acceptor (A-D-A) architecture affects their physical and optoelectronic properties is critical for determining their ultimate performance in organic electronic devices. Here, we utilized femtosecond transient absorption, time-resolved upconversion photoluminescence spectroscopy, and tunable femtosecond-stimulated Raman spectroscopy, aided by quantum chemical calculations, to systematically investigate the excited state structural dynamics of the intramolecular charge transfer of the tetramethoxy anthracene-based fluorophore 2,3,6,7-tetramethoxy 9,10-dibenzaldehydeanthracene (AnDA) and its derivative 2,3,6,7-tetramethoxy 9,10-diphenylanthracene (TMDPAn) in chloroform. In the AnDA molecule, the tetramethoxy anthracene and benzaldehyde moieties exhibit a strong ability to donate and withdraw electrons. Upon photoexcitation, AnDA shows intriguing ultrafast fluorescence switch-on and red shift dynamics on charge transfer states, and the temporal evolution of AnDA recorded by ultrafast spectroscopy reveals a dynamic picture of two-step intramolecular charge transfer assisted by ultrafast conformational changes and solvation processes. Removing the aldehyde group from TMDPAn significantly decreases the electron pulling capacity of the phenyl unit and disables charge transfer characteristics.

Effect of 3d/4p Mixing on 1s2p Resonant Inelastic X-ray Scattering: Electronic Structure of Oxo-Bridged Iron Dimers.

1s2p resonant inelastic X-ray scattering (1s2p RIXS) has proven successful in the determination of the differential orbital covalency (DOC, the amount of metal vs ligand character in each d molecular orbital) of highly covalent centrosymmetric iron environments including heme models and enzymes. However, many reactive intermediates have noncentrosymmetric environments, e.g., the presence of strong metal-oxo bonds, which results in the mixing of metal 4p character into the 3d orbitals. This leads to significant intensity enhancement in the metal K-pre-edge and as shown here, the associated 1s2p RIXS features, which impact their insight into electronic structure. Binuclear oxo bridged high spin Fe(III) complexes are used to determine the effects of 4p mixing on 1s2p RIXS spectra. In addition to developing the analysis of 4p mixing on K-edge XAS and 1s2p RIXS data, this study explains the selective nature of the 4p mixing that also enhances the analysis of L-edge XAS intensity in terms of DOC. These 1s2p RIXS biferric model studies enable new structural insight from related data on peroxo bridged biferric enzyme intermediates. The dimeric nature of the oxo bridged Fe(III) complexes further results in ligand-to-ligand interactions between the Fe(III) sites and angle dependent features just above the pre-edge that reflect the superexchange pathway of the oxo bridge. Finally, we present a methodology that enables DOC to be obtained when L-edge XAS is inaccessible and only 1s2p RIXS experiments can be performed as in many metalloenzyme intermediates in solution.

Probing the Electronic Band Gap of Solid Hydrogen by Inelastic X-Ray Scattering up to 90 GPa.

Metallization of hydrogen as a key problem in modern physics is the pressure-induced evolution of the hydrogen electronic band from a wide-gap insulator to a closed gap metal. However, due to its remarkably high energy, the electronic band gap of insulating hydrogen has never before been directly observed under pressure. Using high-brilliance, high-energy synchrotron radiation, we developed an inelastic x-ray probe to yield the hydrogen electronic band information in situ under high pressures in a diamond-anvil cell. The dynamic structure factor of hydrogen was measured over a large energy range of 45 eV. The electronic band gap was found to decrease linearly from 10.9 to 6.57 eV, with an 8.6 times densification (ρ/ρ_{0}∼8.6) from zero pressure up to 90 GPa.

The five-analyzer point-to-point scanning crystal spectrometer at ESRF ID26.

X-ray emission spectroscopy in a point-to-point focusing geometry using instruments that employ more than one analyzer crystal poses challenges with respect to mechanical design and performance. This work discusses various options for positioning the components and provides the formulas for calculating their relative placement. Ray-tracing calculations were used to determine the geometrical contributions to the energy broadening including the source volume as given by the beam footprint on the sample. The alignment of the instrument is described and examples are given for the performance.

Resonant X-ray emission spectroscopy from broadband stochastic pulses at an X-ray free electron laser.

Hard X-ray spectroscopy is an element specific probe of electronic state, but signals are weak and require intense light to study low concentration samples. Free electron laser facilities offer the highest intensity X-rays of any available light source. The light produced at such facilities is stochastic, with spikey, broadband spectra that change drastically from shot to shot. Here, using aqueous ferrocyanide, we show that the resonant X-ray emission (RXES) spectrum can be inferred by correlating for each shot the fluorescence intensity from the sample with spectra of the fluctuating, self-amplified spontaneous emission (SASE) source. We obtain resolved narrow and chemically rich information in core-to-valence transitions of the pre-edge region at the Fe K-edge. Our approach avoids monochromatization, provides higher photon flux to the sample, and allows non-resonant signals like elastic scattering to be simultaneously recorded. The spectra obtained match well with spectra measured using a monochromator. We also show that inaccurate measurements of the stochastic light spectra reduce the measurement efficiency of our approach.

A compact extreme ultraviolet high-throughput spectrometer based on the multilayer varied-line-spacing grating.

In this paper, we propose a compact extreme ultraviolet high-throughput spectrometer covering the 50-70 eV energy band. The key element in this spectrometer is a multilayer varied-line-spacing grating that operates in near-normal incidence geometry. The spectrometer can obtain one order of magnitude higher throughput compared to the traditional grazing incidence grating spectrometer in this energy band. The spectrum collection time and sample radiation damage can be largely reduced using the presented design.

Resonant X-ray emission spectroscopy from broadband stochastic pulses at an X-ray free electron laser.

Hard X-ray spectroscopy is an element specific probe of electronic state, but signals are weak and require intense light to study low concentration samples. Free electron laser facilities offer the highest intensity X-rays of any available light source. The light produced at such facilities is stochastic, with spikey, broadband spectra that change drastically from shot to shot. Here, using aqueous ferrocyanide, we show that the resonant X-ray emission (RXES) spectrum can be inferred by correlating for each shot the fluorescence intensity from the sample with spectra of the fluctuating, self-amplified spontaneous emission (SASE) source. We obtain resolved narrow and chemically rich information in core-to-valence transitions of the pre-edge region at the Fe K-edge. Our approach avoids monochromatization, provides higher photon flux to the sample, and allows non-resonant signals like elastic scattering to be simultaneously recorded. The spectra obtained match well with spectra measured using a monochromator. We also show that inaccurate measurements of the stochastic light spectra reduce the measurement efficiency of our approach.