Terahertz charge transport dynamics in 3D graphene networks with localization and band regimes.

Terahertz steady-state and time-resolved conductivity and permittivity spectra were measured in 3D graphene networks assembled in free-standing covalently cross-linked graphene aerogels. Investigation of a transition between reduced-graphene oxide and graphene controlled by means of high-temperature annealing allowed us to elucidate the role of defects in the charge carrier transport in the materials. The THz spectra reveal increasing conductivity and decreasing permittivity with frequency.

Biochemical and SSR based molecular characterization of elite rice varieties for straw lignocellulose.

Background: Lignocellulosic biomass from rice straw possesses enormous potential in generating bioenergy thereby reducing the dependence of human on non-renewable fuel sources. Developing rice varieties of such calibre necessitates biochemical characterization as well as assessing the presence of genetic diversity among the rice genotypes with respect to cellulose content.

Methods And Results: Forty-three elite rice genotypes were selected for biochemical characterization and SSR marker-based genetic fingerprinting.

Comprehensive Study of All-Solid-State Z-Scheme Photocatalytic Systems of ZnO/Pt/CdZnS.

We have investigated a Z-scheme based on a ZnO/Pt/CdZnS photocatalyst, active in the presence of a complex medium composed of acetic acid and benzyl alcohol, the effects of which on the catalyst stability and performance are studied. Transmission electron microscopy images showed uniformly dispersed sub-nanometer Pt particles. Inductively coupled plasma and X-ray photoelectron spectroscopy analyses suggested that Pt is sandwiched between ZnO and CdZnS.

Direct versus ligand-exchange synthesis of [PtAg(BDT)(TPP)] nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties.

Heteroatom doping of atomically precise nanoclusters (NCs) often yields a mixture of doped and undoped products of single-atom difference, whose separation is extremely difficult. To overcome this challenge, novel synthesis methods are required to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg NCs produces a mixture of [Ag(BDT)(TPP)] and [PtAg(BDT)(TPP)] NCs (TPP: triphenylphosphine; BDT: 1,3-benzenedithiolate).

Direct-Indirect Nature of the Bandgap in Lead-Free Perovskite Nanocrystals.

With record efficiencies achieved in lead halide perovskite-based photovoltaics, urgency has shifted toward finding alternative materials that are stable and less toxic. Bismuth-based perovskite materials are currently one of the most promising candidates among those alternatives. However, the band structures of these materials, including the nature of the bandgaps, remain elusive due to extremely low photoluminescence quantum yield (PLQY) and scattering issues in their thin-film form.

Doping-Induced Anisotropic Self-Assembly of Silver Icosahedra in [PtAgCl(PPh)] Nanoclusters.

Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [PtAgCl(PPh)].

Engineering Interfacial Charge Transfer in CsPbBr Perovskite Nanocrystals by Heterovalent Doping.

Since compelling device efficiencies of perovskite solar cells have been achieved, investigative efforts have turned to understand other key challenges in these systems, such as engineering interfacial energy-level alignment and charge transfer (CT). However, these types of studies on perovskite thin-film devices are impeded by the morphological and compositional heterogeneity of the films and their ill-defined surfaces. Here, we use well-defined ligand-protected perovskite nanocrystals (NCs) as model systems to elucidate the role of heterovalent doping on charge-carrier dynamics and energy level alignment at the interface of perovskite NCs with molecular acceptors.

pH-Induced Surface Modification of Atomically Precise Silver Nanoclusters: An Approach for Tunable Optical and Electronic Properties.

Noble metal nanoclusters (NCs) play a pivotal role in bridging the gap between molecules and quantum dots. Fundamental understanding of the evolution of the structural, optical, and electronic properties of these materials in various environments is of paramount importance for many applications. Using state-of-the-art spectroscopy, we provide the first decisive experimental evidence that the structural, electronic, and optical properties of Ag(MNBA) NCs can now be tailored by controlling the chemical environment.

Shape-Tunable Charge Carrier Dynamics at the Interfaces between Perovskite Nanocrystals and Molecular Acceptors.

Hybrid organic/inorganic perovskites have recently emerged as an important class of materials and have exhibited remarkable performance in photovoltaics. To further improve their device efficiency, an insightful understanding of the interfacial charge transfer (CT) process is required. Here, we report the first direct experimental observation of the tremendous effect that the shape of perovskite nanocrystals (NCs) has on interfacial CT in the presence of a molecular acceptor.

Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis.

A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multitopic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity toward hydrogen-evolution reaction (HER) with remarkable recyclability.

Real-Space Mapping of Surface Trap States in CIGSe Nanocrystals Using 4D Electron Microscopy.

Surface trap states in copper indium gallium selenide semiconductor nanocrystals (NCs), which serve as undesirable channels for nonradiative carrier recombination, remain a great challenge impeding the development of solar and optoelectronics devices based on these NCs. In order to design efficient passivation techniques to minimize these trap states, a precise knowledge about the charge carrier dynamics on the NCs surface is essential. However, selective mapping of surface traps requires capabilities beyond the reach of conventional laser spectroscopy and static electron microscopy; it can only be accessed by using a one-of-a-kind, second-generation four-dimensional scanning ultrafast electron microscope (4D S-UEM) with subpicosecond temporal and nanometer spatial resolutions.

Real-Space Visualization of Energy Loss and Carrier Diffusion in a Semiconductor Nanowire Array Using 4D Electron Microscopy.

A breakthrough in the development of 4D scanning ultrafast electron microscopy is described for real-time and space imaging of secondary electron energy loss and carrier diffusion on the surface of an array of nanowires as a model system, providing access to a territory that is beyond the reach of either static electron imaging or any time-resolved laser spectroscopy.

Gold Doping of Silver Nanoclusters: A 26-Fold Enhancement in the Luminescence Quantum Yield.

A high quantum yield (QY) of photoluminescence (PL) in nanomaterials is necessary for a wide range of applications. Unfortunately, the weak PL and moderate stability of atomically precise silver nanoclusters (NCs) suppress their utility. Herein, we accomplished a ≥26-fold PL QY enhancement of the Ag29 (BDT)12 (TPP)4 cluster (BDT: 1,3-benzenedithiol; TPP: triphenylphosphine) by doping with a discrete number of Au atoms, producing Ag29-x Aux (BDT)12 (TPP)4 , x=1-5.

Air-Stable Surface-Passivated Perovskite Quantum Dots for Ultra-Robust, Single- and Two-Photon-Induced Amplified Spontaneous Emission.

We demonstrate ultra-air- and photostable CsPbBr3 quantum dots (QDs) by using an inorganic-organic hybrid ion pair as the capping ligand. This passivation approach to perovskite QDs yields high photoluminescence quantum yield with unprecedented operational stability in ambient conditions (60 ± 5% lab humidity) and high pump fluences, thus overcoming one of the greatest challenges impeding the development of perovskite-based applications. Due to the robustness of passivated perovskite QDs, we were able to induce ultrastable amplified spontaneous emission (ASE) in solution processed QD films not only through one photon but also through two-photon absorption processes.

Templated Atom-Precise Galvanic Synthesis and Structure Elucidation of a [Ag24Au(SR)18](-) Nanocluster.

Synthesis of atom-precise alloy nanoclusters with uniform composition is challenging when the alloying atoms are similar in size (for example, Ag and Au). A galvanic exchange strategy has been devised to produce a compositionally uniform [Ag24Au(SR)18](-) cluster (SR: thiolate) using a pure [Ag25(SR)18](-) cluster as a template. Conversely, the direct synthesis of Ag24Au cluster leads to a mixture of [Ag(25-x)Au(x)(SR)18](-), x=1-8.

To what extent can charge localization influence electron injection efficiency at graphene-porphyrin interfaces?

Controlling the electron transfer process at donor-acceptor interfaces is a research direction that has not yet seen much progress. Here, with careful control of the charge localization on the porphyrin macrocycle using β-cyclodextrin as an external cage, we are able to improve the electron injection efficiency from cationic porphyrin to graphene carboxylate by 120%. The detailed reaction mechanism is also discussed.

Ultrafast electron injection at the cationic porphyrin-graphene interface assisted by molecular flattening.

The steady-state and femtosecond (fs) time-resolved data clearly demonstrate that the charge transfer (CT) process at the porphyrin-graphene carboxylate (GC) interfaces can be tuned from zero to very sufficient and ultrafast by changing the electronic structure of the meso unit and the redox properties of the porphyrin cavity.