Intrinsic Charge Transfer Research Articles

NiFe-spinel oxides with nitrogen-doped carbon quantum dots for enhanced oxygen evolution activity

Designing efficient and stable electro-catalysts for non-precious metal oxygen evolution reactions (OER) is critical to solve the bottleneck of water splitting. The NiFe2O4/NCQDs composite electrode was fabricated by combining nitrogen doped carbon quantum dots (NCQDs) with NiFe2O4 spinel via a hydrothermal method, which showed brilliant OER catalytic performance by modifying on nickel foams (NF). The composites had petal-like structures, and the NiFe2O4 was epitaxially grown on the NF substrates with exposed sites, resulting in enhanced electron transport. The fluorescence quenching of NCQDs was accompanied by binding NCQDs with NiFe2O4, which indicated the energy barrier was greatly reduced during the electron transport as well as electro-catalysis. The higher intrinsic charge transfer was achieved, and the doping combination having a higher conductivity was confirmed. The electrochemical activity of NiFe2O4/NCQDs electrode in OER reaction was evaluated under alkaline conditions. The addition of NCQDs effectively enhanced the OER activity, and over-potentials were decreased from 330 mV to 270 mV at 10 mA cm−2 with Tafel slope lower (66 mV/dec) than counterparts. The NiFe2O4/NCQDs displayed long-term catalytic stability at 1.47 V. Therefore, a facile method for preparing NiFe2O4/NCQDs was developed which had characteristics of low cost, simple process and excellent OER activity.

Enhanced electrochemical performances of ternary polypyrrole/MXene/Gum arabic composites as supercapacitors electrode materials

The development of supercapacitor electrodes for high energy storage applications requires the use of ternary composites made of PPy, Mxene, Gum Arabic (PPy/Mxene/GA) these materials are special because they have new characteristics like cyclic stability, and high specific capacitance. The pure PPy, PPy/Mxene and PPy/Mxene/Gum Arabic show the shifting and appearance of new peaks in UV-Visible spectra, which are further supported by the Fourier transform infrared spectroscopy (FT-IR). The appearance of new peaks in X-ray diffraction (XRD) of PPy confirms presence of Mxene and Gum Arabic, which is in agreement with the energy dispersive X-ray (EDX) analysis. The electrochemical techniques such as Cyclic Voltammetry (CV), Galvanostatic Charge Discharge (GCD) and Electrochemical Impedance Spectroscopy (EIS) show that the (PPy/Mxene/GA) ternary composite maintains 94 % of the specific capacitance retention after 2000 cycles and; reaches a maximum specific capacitance of 657.64 F/g at 1 A/g. As compared to Pure PPy and PPy/Mxene composite the PPy/Mxene/GA composite show small intrinsic resistance Rs and charge transfer Rct values 0.11Ω and 6.15Ω respectively. The outstanding electrochemical properties of PPy/Mxene/GA composite are ascribed to the blending of three different type compounds PPy, Mxene and GA and theirs mutual beneficial effects. These findings show that ternary composite material holds great promise for use in these condition involving portable electronic storage devices.

Heteroatom-doped cobalt single-atomic nanozymes with differential enzyme-like activity for bacteria-infected wound therapy

Single-atom nanozymes (SANZs) have emerged as new media for enhancing chemodynamic therapy (CDT) to achieve desirable enzyme-like effects and excellent nanoscale specificity. However, non-optimal adsorption of Fenton-like reaction intermediates prevents SANZs from exerting kinetic activity and hinders the CDT effect. Herein, we demonstrate that heteroatom-doped Co single-atom nanozymes (SACNZs) with intrinsic charge transfer exhibit peroxidase-like properties and significantly improve the ability of CDT to treat Staphylococcus aureus-infected wounds. Density functional theory calculations showed that the S-induced charge transfer effect regulated the electronic distribution of the central metal more efficiently than P, thereby lowering the energy levels for the generation of OH and increasing the catalytic effect. Polyvinylpyrrolidone-modified SACNZs showed effects consistent with this theory in both in vitro antibacterial and in vivo ward management assays. This study systematically investigated the relationship between heteroatom-doping and the catalytic activity of metal centres, opening a new perspective for the application of CDT.

Chemomechanics Engineering Promotes the Catalytic Activity of Spinel Oxides for Sulfur Redox Reaction

AbstractCooperative catalysis is a promising approach to enhance the sluggish redox kinetics of lithium polysulfides (LiPSs) for practical lithium–sulfur (Li–S) batteries. However, the elusory synergistic effect among multiple active sites makes it challenging to accurately customize the electronic structure of catalysts. Herein, a strategy of precisely tailoring eg orbitals of spinel oxides through chemomechanics engineering is porposed to regulate LiPSs retention and catalysis. By manipulating the regulable cations in MnxCo3‐xO4, it is theoretically and experimentally revealed that the lattice strain induced by the Jahn–Teller active and high‐spin Mn3+ at octahedral (Oh) sites can increase the eg occupancy of low‐spin Co3+Oh, which effectively regulates the chemical affinity toward LiPSs and establishes an unblocked channel for intrinsic charge transfer. This leads to a volcano‐type correlation between the eg occupancy at Oh sites and sulfur redox activity. Benefitting from the cooperative catalysis of dual‐active sites, MnCo2O4 with an average eg occupancy of 0.45 affords the most appropriate adsorption strength and rapid redox kinetics toward LiPSs, leading to remarkable rate performance and capacity retention for the assembled Li–S batteries. This work demonstrates the promise of chemomechanics engineering for optimizing the eg occupancy to achieve efficient sulfur redox catalysts.

Flexible bifunctional electrocatalyst (Ni@(Ni,Fe)Se2/Ni@CC) by adjusting d-band center for high-efficiency HER and overall water splitting

Nickel foam is widely used as a collector for electrocatalysts because of its excellent electrical conductivity; however, it is prone to react with elements such as oxygen, sulfur, and phosphorus during the growth of electrode materials, which makes it brittle and fragile, thus limiting its large-scale application. In this study, bifunctional electrocatalysts with flexible multilevel Ni-based nanoclusters Ni@(Ni,Fe)Se2/Ni@CC were synthesized on carbon cloth (CC) by hydrothermal and electrodeposition methods; these flexible electrocatalysts are convenient for subsequent industrial applications. At a current density of 10 mA cm−2, the overpotentials of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) reached 98 and 224 mV, respectively, exceeding the catalytic effects of most metal-based collectors. The overall water-splitting potential of the catalyst was only 1.56 V at 10 mA cm−2, and the performance was maintained after a 24 h stability test. Ni@(Ni,Fe)Se2/Ni@CC significantly improved the activity in alkaline environments by modulating the center of the d-band, thereby increasing the adsorption capacity of the catalyst for H ions. In this study, we improved the intrinsic activity and charge transfer of transition metal electrocatalysts by modifying the carbon cloth and constructing multilevel Ni-based nanoclusters, which provided some insights into the rational design of flexible bifunctional electrocatalysts.

Addressing adsorption and catalysis of lithium polysulfide via electronic distribution of molybdenum carbide host

Heterostructure engineering is considered a crucial strategy to modulate the intrinsic charge transfer behavior of materials, enhance catalytic activity, and optimize sulfur electrochemical processes. However, parsing the role of heterogeneous interface-structure–property relationships in heterostructures is still a key scientific issue to realize the efficient catalytic conversion of polysulfides. Based on this, molybdenum carbide (Mo2C) was successfully partial reduced to molybdenum metal (Mo) via a thermal reduction at high-temperature and the typical Mo-Mo2C-based Mott-Schottky heterostructures were simultaneously constructed, which realized the modulation of the electronic structure of Mo2C and optimized the conversion process of lithium polysulfides (LPS). Compared with single molybdenum carbide, the modulated molybdenum carbide acts as an electron donor with stronger Mo-S bonding strength as well as higher polysulfide adsorption energy, faster Li2S conversion kinetics, and greatly facilitates the adsorption → catalysis process of LPS. As a result, yolk-shell Mo-Mo2C heterostructure (C@Mo-Mo2C) exhibits excellent cycling performance as a sulfur host, with a discharge specific capacity of 488.41 mAh g−1 for C@Mo-Mo2C/S at 4 C and present an excellent high-rate cyclic performance accompanied by capacity decay rate of 0.08 % per cycle after 400 cycles at 2 C. Heterostructure-acting Mo2C electron distribution modulation engineering may contributes to the understanding of the structure-interface-property interaction law in heterostructures and further enables the efficient modulation of the chemical behavior of sulfur.

Atomic-scale visualization of the interlayer Rydberg exciton complex in moiré heterostructures

Excitonic systems, facilitated by optical pumping, electrostatic gating or magnetic field, sustain composite particles with fascinating physics. Although various intriguing excitonic phases have been revealed via global measurements, the atomic-scale accessibility towards excitons has yet to be established. Here, we realize the ground-state interlayer exciton complexes through the intrinsic charge transfer in monolayer YbCl3/graphite heterostructure. Combining scanning tunneling microscope and theoretical calculations, the excitonic in-gap states are directly profiled. The out-of-plane excitonic charge clouds exhibit oscillating Rydberg nodal structure, while their in-plane arrangements are determined by moiré periodicity. Exploiting the tunneling probe to reflect the shape of charge clouds, we reveal the principal quantum number hierarchy of Rydberg series, which points to an excitonic energy-level configuration with unusually large binding energy. Our results demonstrate the feasibility of mapping out the charge clouds of excitons microscopically and pave a brand-new way to directly investigate the nanoscale order of exotic correlated phases.

Photothermionic Effect-Assisted Ultrafast Charge Transfer in NbS2/MoS2 Heterostructure.

Two-dimensional (2D) van der Waals heterostructures (vdW HSs) composed of transition metal dichalcogenides (TMDCs) have emerged as frontrunners in the optoelectronics field, owing to their exceptional optical and electrical properties. Recent research on the intrinsic interlayer charge transfer mechanism has been primarily focused on the Type II HSs, while metal-semiconductor (MS) vertical HSs, promising for advancing photodetector technology, have received comparatively less attention. Here, we reveal the first experimental observation of photothermionic effect-assisted ultrafast interlayer charge transfer in the NbS2/MoS2 heterostructure using femtosecond transient absorption technology and first-principles calculations, effectively ignoring the Schottky barrier height. We demonstrate that within 500 fs, charge transfer occurs from NbS2 to MoS2 in the heterostructure, resulting in supplementary carrier generation in the visible spectrum when excited with infrared light below the MoS2 bandgap, at wavelengths of 1030 and 1500 nm. Such promising characteristics of 2D NbS2-semiconductor heterostructures offer a potential platform for synergistically combining low contact resistance with broadband photocarrier generation, marking a significant advancement in optoelectronics and light harvesting.

(Keynote) Experimental and Computational Insights into Electronic Structure and Redox Properties of Bare and Doped Co3O4 Nanocrystals of Euhedral Morphology and Their Heterojunctions with Alien Oxides and Carbon Materials

One of the most attractive oxide materials with remarkable record of widespread applications are cobalt spinels and their derivatives obtained by doping with alien redox (3dn) and nonredox (Li) cations or via hybridization with other oxides (CeO2, TiO2, a-Al2O3) or carbon support. They have recently received a great deal of theoretical and practical attention because of an outstanding activity in many redox processes important for photo/electro/catalysis. Among many potential applications, their relevance as promising substitutes for platinum in oxygen reduction reaction (ORR) or oxygen evolution reaction (OER) can be mentioned, in particular. The properties of nanostructured cobalt spinel materials depend on their size, shape, doping and interfacing features. In this context, euhedral spinel nanocrystals that expose well defined crystallographic planes, allow for sensible investigations into establishment of the surface/bulk structure-redox reactivity relationships in real conditions.In this presentation application of S/TEM and inverse Wulff hull matching techniques supported by image simulation was discussed for elucidation the mechanism of hydrothermal synthesis of euhedral cobalt spinel nanocrystals the their shape retrieving. Periodic spin unrestricted DFT-PW91+U and hybrid DFT/HSE06 calculations were applied for modeling the morphology, structure and electronic properties (DOS structure) relevant for redox behavior of bare and doped cobalt spinel nanocrystals. The results allowed for thorough characterization of the structure and reconstruction of the exposed low index (100), (110), and (111) planes, and explain the influence of dopants. The effect of the valence state of lithium (Li+ or Li0), and its locus on the valence pining of the cobalt cations was determined. DFT calculations together with the ab initio thermodynamic modeling were used to study the electronic structure of the created defects, and stability of different terminations of cobalt spinel and Li-doped Co3O4 under various redox conditions. The associated electronic and spin relaxation processes were discussed as well. For the most stable stoichiometric (100) and (111) facets, the surface redox state diagrams in a wide stoichiometry range were constructed, and analyzed in detail. Intrinsic charge transfer processes involving electron (n-conductivity) and hole (p-conductivity) transfer between the octahedral and tetrahedral cobalt cations were modeled using a small polaron approximation (Marcus-Dupuis model). Formation of n-p junctions (Co3O4|CeO2, Li-Co3O4|CeO2) and MxCo3-xO4/carbon hybrids were analyzed by S/TEM, XPS spectroscopy (band alignment), contactless electronic conductivity and work function measurements, corroborated by DFT modeling. The redox properties of the interface and spinel faceting, and the role of electric conductivity and the nature of the carbon support functional groups were discussed in the context of the ORR, OER performance, and catalytic redox reactivity (activation of O2).AcknowledgmentsS.W. thanks for the financial support of the project “High-performance electrocatalyst for oxygen reduction reaction with low platinum content” carried on within the Program “Pearls of Science” of the Ministry of Education and Science of Poland.

Amorphous and crystalline interface engineering of FeSeOx/Mo-NiSe2 nanoarrays for synergistically boosting electrocatalytic water oxidation

Exploring integrated regulation strategies to boosting electrocatalytic performance is essential to design more efficient and inexpensive OER catalysts. Herein, amorphous and crystalline (a-c) interface engineering and heteroatom doping are integrated to construct a novel electrocatalyst containing amorphous FeSeOx and crystalline Mo-doped NiSe2 (denoted as FeSeOx/Mo-NiSe2) via pseudocrystalline replication method and selenization treatment. The resultant FeSeOx/Mo-NiSe2 electrocatalyst with 3D hierarchical nanoarchitectures of nanorod arrays covered by interlocking nanoblocks exposes more active sites and accelerated reaction kinetics. Furthermore, a-c interface engineering and heteroatom doping can synergistically enhance the intrinsic activity and charge transfer capability of NiSe2 by decreasing the electron diffusion distance and flexibly modulating the electronic structure, which contributes to boost the oxygen evolution reaction (OER) performance. Consequently, the obtained FeSeOx/Mo-NiSe2 achieves a low overpotential of 205 mV at 10 mA cm−2, which outperforms many other transitions metal selenides electrocatalysts. Density functional theory (DFT) calculations demonstrate that the formation of an internal electric field between FeSeOx and Mo-NiSe2 accelerates charge transport and optimizes the adsorption/desorption of oxygen-containing intermediates, thereby accelerating the reaction kinetics and improving the OER performance. This work serves as a point of reference for designing innovative metal selenides based electrocatalysts combining a-c interface engineering and heteroatom doping.

End-capped engineering of carbazole based dopant free hole transporting material with improved power conversion efficiency

Perovskite solar cells (PSCs) belonging to third-generation of solar cells are reported to have better power conversion efficiency, cost-effectiveness, and many other benefits. This computational investigation focuses on designing five indolo(3,2-b) carbazole (ICZ) central core containing small hole transport materials (HTMs) to discover photovoltaic properties as donors for perovskite solar cells accompanied by enhanced charge mobility. New HTMs with A–π–D–π–A skeleton has been designed by thiophene-bridged end-capped acceptor engineering on reference molecule (ICZ-R). Absorption spectra, frontier MOs, density of state analysis, molecular electrostatic potential surfaces, transition density matrix, non-covalent interactions, iso-surface maps, and planarity parameters were analyzed through different softwares for better-predicting performance of perovskite solar cells. All tailored HTMs showed better absorption profiles. Among them, ICZ-D3 exhibited the maximum absorbance λmax at 695 nm in dichloromethane solvent and the greatest full-width half maximum (313.93 nm). ICZ-D2 showed the lowest Eg of 1.62 eV, and the highest dipole moment (8.35 D) in the solvent phase, showing admirable solubility. Designed HTMs exhibited decelerated HOMO values (−4.62 to −5.25), lower values of binding energies (0.0323–0.388 <0.542 eV), better intrinsic charge transfer percentage (10.74–72.71%>7.88), lower hardness (0.81–1.11 <1.78 eV) and greater softness values (0.90–1.23 >0.56 eV) as compared to ICZ-R. All designed HTMs demonstrated higher estimated VOC and power conversion efficiency (PCE=11.81–25.90%) than ICZ-R, leading to fruitful applications. ICZ-D4 resulted in the highest PCE (25.90%) with better VOC (1.25 eV). These outstanding findings paved a new way to develop better-performing HTMs for PSCs.

Ambipolar charge transfer of larger fullerenes enabled by the modulated surface potential of h-BN/Rh(111)

A detailed understanding of how molecules interact with two-dimensional materials, particularly concerning energy level alignment and charge transfer processes, is essential to incorporate functional molecular films into next-generation 2D material-organic hybrid devices. One of the major challenges in integrating molecular films in field-effect transistors is facilitating ambipolar charge transport, which is often hindered by the large electronic gap of the organic layers. This work compares the adsorption site-dependent energy level alignment of C60, C70, and C84 fullerenes induced by the spatial variation of the electrostatic surface potential of the h-BN/Rh(111) Moiré superstructure. As the size of the fullerenes increases, the HOMO-LUMO gap shrinks. In the case of C84, we find an intrinsic charge transfer from the substrate to the fullerenes adsorbed in the Moiré pore centers, rendering them negatively charged. The electric field effect-induced charging of neutral fullerenes and discharging of intrinsically negatively charged fullerenes are investigated using scanning tunneling spectroscopy, non-contact atomic force microscopy, and Kelvin probe force spectroscopy. Our findings show that on metal-supported h-BN, the LUMO level of C84 is sufficiently close to the Fermi energy that it can be neutral or 1e− negatively charged depending on slight variations of the electrostatic potential. The findings propose a path to make ambipolar charge transfer accessible and efficient by circumventing the need to overcome the fullerenes’ electronic gap.

S-scheme heterojunctions based on novel Sm2CeMnO6 double perovskite oxide and g-C3N4 with excellent photocatalytic dye degradation performances.

It has become of utmost importance to preserve marine life and human health by protecting aquatic environments from contaminants. Therefore, using photocatalytic materials in treatment of contaminated water is a promising and innovative technique. Novel double perovskite Sm2CeMnO6 was synthesized through a modified Pechini sol-gel method. Also, urea and melamine were utilized to synthesize graphitic carbon nitride (g-C3N4). Combination of Sm2CeMnO6 and g-C3N4 produced several S-scheme heterojunction materials in diverse components ratios. Average crystallite sizes of Sm2CeMnO6 and Sm2CeMnO6/g-C3N4 (20:80) samples were calculated by Debye-Scherrer and Williamson-Hall methods to be 19.77, 22.72 nm and 42.01, 43.73 nm, respectively. The coexistence of g-C3N4 (002) with a d-spacing of 0.325 nm and Sm2CeMnO6 planes of (222), (111), and (400) with spacing values of 0.314, 0.302, and 0.294 nm, respectively, was depicted in the HR-TEM image of the Sm2CeMnO6/g-C3N4 (20:80). The estimated bandgaps for the g-C3N4, Sm2CeMnO6, and Sm2CeMnO6/g-C3N4 (20:80) were 2.70, 2.60, and 2.65eV, respectively. Their application was investigated in photocatalytic degradation of methylene blue (MB) dye as typical pollutant. The estimated degradation pathway of MB was also provided through LC-MS analysis. Under the identical conditions, the best photocatalytic performance was found for Sm2CeMnO6/g-C3N4 (20:80) composite. Using response surface methodology (RSM), operational parameters of the photocatalytic degradation were modeled and optimized by the best composite through central composite design approach. Applying optimized parameters led to 96% degradation of MB (8 mg/L) at pH 10 under 120 min visible light irradiation (λ > 365 nm) using 0.15 g of Sm2CeMnO6/g-C3N4 (20:80) composite in 100 mL aqueous solution. Due to low intrinsic charge transfer resistance, modified Eg, and good performance in e‒/h+ pairs production, Sm2CeMnO6/g-C3N4 (20:80) nanocomposite was introduced as a promising S-scheme photocatalyst.

Ferroelectric Polarization Modulated Facet-selective Charge Separation in Bi4 NbO8 Cl Single Crystal for Boosting Visible-light Driven Bifunctional Water Splitting.

Developing bifunctional water-splitting photocatalysts is meaningful, but challenged by the harsh requirements of specific-facet single crystals with spatially separated reactive sites and anisotropic charge transfer paths contributed by well-built charge driving force. Herein, tunable ferroelectric polarization is introduced in Bi4 NbO8 Cl single crystal nanosheets to strengthen the orthogonal charge transfer channels. By manipulating the in-plane polarization from octahedral off-centering of Nb5+ and out-of-plane polarization from lone pair electron effect of anisotropic Bi3+ , both the fast charge recombination in bulk catalyst and the process of charge trapping into surface states can be effectively modulated. Collaborating with modest polarization electric field and facet junction induced built-in electric field, cooperative charge tractive force is constructed, which reinforces the spatial separation and migration of photogenerated electrons and holes to {110} reductive site facet and {001} oxidation site facet, respectively. While excessive polarization charges impair the facet-selective charge separation characteristics and conversely promote charge recombination on the surface. As a result, polarity-optimized Bi4 NbO8 Cl shows an excellent H2 and O2 evolution rate of 54.21 and 36.08 μmol ⋅ h-1 in the presence of sacrificial reagents under visible light irradiation. This work unveils the function of ferroelectric polarization in tuning the intrinsic facet-selective charge transfer process of photocatalysts.

The cactus bulb-shaped metal-S-C/N nanoparticles supported by highly conductive channels for efficient electrocatalytic hydrogen evolution reaction

Accelerating electron transfer and exposing active sites are key factors that could improve electrocatalytic hydrogen evolution reaction (HER). In this study, Co3S4-Ni3S2-C/N, the cactus bulb-shaped nanoparticles based on metal-organic frameworks (MOFs), were successfully prepared. The catalyst requires only 101 and 227 mV overpotential to reach current densities of 20 and 100 mA cm−2, respectively, in 1 M KOH. The high catalytic activity is attributed to the confinement effect achieved by introducing 2-aminoterephthalic acid as a precursor, allowing the catalyst to have a small particle size and fully exposed metal active sites. Moreover, the catalyst has a highly conductive metal-S-C/N channel that effectively reduces the intrinsic charge transfer resistance of the catalytic electrode, improves its conductivity, and modulates the electron density at the metal active site. Furthermore, compared to other crystal planes, the exposed (111) crystal plane of Co3S4 provides the most octahedral coordination of high spin state Co3+, which is highly catalytically active. This makes it the dominant crystal plane for catalysis. Through spatial confinement effect to limit metal sulfide particle size and introducing an organic backbone to create highly conductive metal-S-C/N channels, our study provides a general approach to developing highly active catalytic materials.

Blocking Accretion Enables Dimension Reduction of Metal-Organic Framework for Photocatalytic Performance.

The evolution and formation process of two-dimensional metal-organic frameworks (MOFs) primarily arise from the anisotropic growth of crystals, leading to variations in photocatalytic performance. It is crucial to achieve a synergistic combination of anisotropic electron transfer direction and dimension reduction strategies. In this study, a novel approach that effectively blocks crystal growth accretion through the coordination of solvent molecules is presented, achieving the successful synthesis of impurity-free two-dimensional nanosheet Zn-PTC with exceptional hydrogen evolution reaction (HER) performance (15.4mmolg-1 h-1 ). The structural and photophysical characterizations validate the successful prevention of crystal accretion, while establishing correlation between structural anisotropy and intrinsic charge transfer mode through transient spectroscopy. These findings unequivocally demonstrate that electron transfer along the [001] direction plays a pivotal role in the redox performance of nano-Zn-PTC. Subsequently, by coupling the photocatalytic performance and density functional theory (DFT) simulation calculations, the carrier diffusion kinetics is explored, revealing that effective dimension reduction along the ligand-to-metal charge transfer (LMCT) direction is the key to achieving superior photocatalytic performance.

Engineering push–pull structural versatility in highly functional carbazole-based hole transporting materials design for efficient perovskites solar devices

This study proposes a push–pull molecular engineering strategy to design highly functional hole transport materials (HTMs) for perovskite solar cells (PSCs). The strategy involves introducing acceptor-anchor groups via benzene spacer to the versatile carbazole core containing dimethoxytriphenylamine side groups, resulting in a series of nine newly designed HTM moieties (BEN-A1 to BEN-A9). Quantum simulation protocols using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods were employed to investigate the designed HTMs. Our results demonstrate that the designed HTMs exhibit promising charge separation and transport throughout the molecule with lower spatial hole-electron overlap at the carbazole core, resulting in 98% intrinsic charge transfer and small exciton binding energy (0.003–0.108 eV). The HTMs also exhibit stabilized HOMO energy levels (by up to 0.13 eV) approaching the threshold (−5.38 eV) with appropriate HTM/Perovskite energy levels alignment, suggesting excellent charge extraction and higher VOC. Optical analysis shows that our proposed HTMs exhibit large stokes shift values (82–108 nm) and transparent absorption in broader visible region, enabling full utilization of light for perovskite layer for photocurrent generation, efficient energy conversion, reduced thermalization losses, and improved spectral selectivity. The HTMs exhibit smaller hole reorganization energy (0.111–0.137 eV) and higher transfer integral, indicating robust hole mobility owing to enhanced carbazole core functionality. Furthermore, higher negative solvation-free energy values (−16.19 to −20.89 kcal/mol) and elevated dipole moments imply better solubility and surface-wetting properties. Overall, this study broadens our understanding of push–pull molecular engineering for versatile carbazole-based HTMs, which have immense prospects for efficient and functional application in PSCs.

Synthesis and characterization of rGO wrapped 1-D NiO nanofibers for ammonia gas sensing application

The fabrication of reduced graphene oxide (rGO) based metal oxide semiconductor (MOS) nanocomposites for applications at room temperature gas sensing have attracted growing interest in during recent years. The present work, one dimensional (1-D) rGO-NiO nano fibers were fabricated by employing electrospinning technique for detection of NH3 gas at room temperature. SEM, XRD, BET, DRS and XPS were used to analyse the surface morphology, structure, composition of materials and optical properties of rGO-NiO nanofibers. Ammonia gas is detected by the rGO-NiO sensor with an excellent response time of 32 s. and recovery time of 38 s. respectively for a concentration of 50 ppm at room temperature. The intrinsic charge transfer due to the synergistic effect of the heterostructure will enhance the sensing performance.

Electronic structure of cuprate–nickelate infinite-layer heterostructure

The discovery of superconductivity in Sr/Ca-doped infinite-layer nickelates Nd(La)NiO2 thin films inspired extensive experimental and theoretical research. However, research on the possibilities of enhanced critical temperature by interface heterostructure is still lacking. Due to the similarities of the crystal structure and band structure of infinite-layer nickelate LaNiO2 and cuprate CaCuO2, we investigate the crystal, electronic and magnetic properties of LaNiO2:CaCuO2 heterostructure using density functional theory and dynamical mean-field theory. Our theoretical results demonstrate that, even a very weak inter-layer z-direction bond is formed, an intrinsic charge transfer between Cu-3d x 2–y 2 and Ni-3d x 2–y 2 orbitals is obtained. The weak interlayer hopping between Cu and Ni leaves a parallel band contributed by Ni/Cu-3d x 2–y 2 orbitals near the Fermi energy. Such an infinite-layer heterostructure with negligible interlayer interaction and robust charge transfer opens a new way for interface engineering and nickelate superconductors.

Dodecahedron CsPbBr3 Perovskite Nanocrystals Enable Facile Harvesting of Hot Electrons and Holes

This Letter reports the facile harvesting of hot carriers (HCs) in a composite of 12-faceted dodecahedron CsPbBr3 nanocrystal (NC) and a scavenger molecule. We recorded ∼3.3 × 1011 s-1 HC cooling rate in NC when excited with ∼1.4 times the band gap energy (Eg), increasing to >3 × 1012 s-1 in the presence of scavengers at high concentration due to the HC extractions. Since the observed intrinsic charge transfer rate (∼1.7 × 1012 s-1) in our NC-scavenger complex is about an order of magnitude higher than the HC cooling rate (∼3.3 × 1011 s-1), carriers are harvested before their cooling. Further, a fluorescence correlation spectroscopy study reveals NC tends to form a quasi-stable complex with a scavenger molecule, ensuring charge transfer completed (τct ≈ 0.6 ps) much before the complex breaks apart (>600 μs). The overall results of our study highlight the promise shown by 12-faceted NCs and their implications in modern applications, including hot carrier solar cells.