Metastable Facet-Controlled Cu2WS4 Single Crystals with Enhanced Adsorption Activity for Gaseous Elemental Mercury.

Purposively designing environmental advanced materials and elucidating the underlying reactivity mechanism at the atomic level allows for the further optimization of the removal performance for contaminants. Herein, using well facet-controlled I-Cu2WS4 single crystals as a model transition metal chalcogenide sorbent, we investigated the adsorption performance of the exposed facets toward gaseous elemental mercury (Hg0). We discovered that the decahedron exhibited not only facet-dependent adsorption properties for Hg0 but also recrystallization along the preferential [001] growth direction from a metastable state to the steady state. Besides, the metastable crystals with a predominant exposure of {101} facets dominated the promising adsorption efficiency (about 99% at 75 °C) while the saturated adsorption capacity was evaluated to be 2.35 mg·g-1. Subsequently, comprehensive characterizations and X-ray adsorption fine structure (XAFS), accompanied by density functional theory (DFT) calculations, revealed that it might be owing to the coordinatively unsaturated local environment of W atoms with S defects and the surface relative stability of different facets, which could be affected by the change in surface atom configuration. Hence, the new insight into the facet-dependent adsorption property of transition metal chalcogenide for Hg0 may have important implications, and the atomic-level study directly provides instructions for development and design of highly efficient functional materials.

Microscopic investigations on the surface-state dependent moisture stability of a hybrid perovskite.

Hybrid organic-inorganic perovskite (HOIP) materials have caught significant attention in photovoltaics and photoelectronics for their outstanding photovoltaic properties. However, their instability to various environment, such as illumination, temperature, moisture and oxygen, hinders their way to commercialization. To figure out the interaction mechanism between H2O and CH3NH3PbI3 (MAPbI3), extensive theoretical studies have been carried out; however, the experimental results are insufficient and inconsistent. Here, we systematically investigate and compare the influence of H2O on MAPbI3 perovskite films with or without DMF) post-annealing in dark or light condition. The interaction between H2O and the surface of pristine MAPbI3 leads to the fusion of grain boundaries thus grain growth into micron level in short-time moisture exposure. While the penetration of H2O into MAPbI3 results in swelled crystalline whisker, cracking into smaller grains in long-time exposure upon the release of H2O. However, no degradation occurs in dark condition. As the DMF post-annealing treatment changes the surface states of MAPbI3, the interactions between the external H2O and internal MAPbI3 significantly varies from the pristine MAPbI3. Three different surface states with different topographies have influence on the interaction process and mechanism with H2O, leading to different decomposition rates, the striped surface that is the most rough among the three and experiencing the minimum change in surface potential with exposure to 80% humidity decomposes into PbI2 fastest. However, the addition of light will once again affect the aforementioned process. It is found that even ambient light could severely speed up the moisture-induced decomposition of MAPbI3, while the N,N-dimethylformamide (DMF) post-annealing treatment significantly improves the stability of MAPbI3 films upon exposure to humidity and illumination, benefiting from the MAI-deficient thus H2O resistant surface.

Interstitial Hydrogen Atom Modulation to Boost Hydrogen Evolution in Pd-Based Alloy Nanoparticles.

Rational control of the components of noble metal alloys is paramount for achieving satisfactory electrocatalytic performances. Though transition metals are commonly used to modify noble metals, many potential elements remain to be explored. Here, we interstitially modulate hydrogen atoms into RhPd nanoparticles to boost the alkaline hydrogen evolution reaction (HER). The obtained stable RhPd-H nanoparticles exhibit pronounced alkaline HER activity with a small overpotential of 36.6 mV at 10 mA cm-2 and a low Tafel slope of 35.3 mV dec-1. The surface electronic state, bond distance, and coordination number of the Rh and Pd atoms are significantly influenced by the presence of interstitial hydrogen atoms. These modifications give RhPd-H nanoparticles a desirable hydrogen adsorption free energy, thus accelerating the hydrogen gas production. We further demonstrate that the interstitial hydrogen atom modulation strategy to improve the HER activity is universal for other Pd-based alloy nanostructures. This work presents a powerful strategy for designing efficient electrocatalysts for the HER and beyond.

PdMo bimetallene for oxygen reduction catalysis.

The efficient interconversion of chemicals and electricity through electrocatalytic processes is central to many renewable-energy initiatives. The sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER)1-4 has long posed one of the biggest challenges in this field, and electrocatalysts based on expensive platinum-group metals are often required to improve the activity and durability of these reactions. The use of alloying5-7, surface strain8-11 and optimized coordination environments12 has resulted in platinum-based nanocrystals that enable very high ORR activities in acidic media; however, improving the activity of this reaction in alkaline environments remains challenging because of the difficulty in achieving optimized oxygen binding strength on platinum-group metals in the presence of hydroxide. Here we show that PdMo bimetallene-a palladium-molybdenum alloy in the form of a highly curved and sub-nanometre-thick metal nanosheet-is an efficient and stable electrocatalyst for the ORR and the OER in alkaline electrolytes, and shows promising performance as a cathode in Zn-air and Li-air batteries. The thin-sheet structure of PdMo bimetallene enables a large electrochemically active surface area (138.7 square metres per gram of palladium) as well as high atomic utilization, resulting in a mass activity towards the ORR of 16.37 amperes per milligram of palladium at 0.9 volts versus the reversible hydrogen electrode in alkaline electrolytes. This mass activity is 78 times and 327 times higher than those of commercial Pt/C and Pd/C catalysts, respectively, and shows little decay after 30,000 potential cycles. Density functional theory calculations reveal that the alloying effect, the strain effect due to the curved geometry, and the quantum size effect due to the thinness of the sheets tune the electronic structure of the system for optimized oxygen binding. Given the properties and the structure-activity relationships of PdMo metallene, we suggest that other metallene materials could show great promise in energy electrocatalysis.

Temperature-Dependent Local Electrical Properties of Organic-Inorganic Halide Perovskites: In Situ KPFM and c-AFM Investigation.

Organic-inorganic halide perovskite materials are emerging as a new class of photoelectric materials for its low cost, easy preparation, and, especially, outstanding optoelectronic properties. Although tremendous efforts have been made on the regulation and optimization of perovskite materials and their microscopic electrical properties for high-efficiency solar cells, few reports focus on the evolution of electrical properties with temperature changes, especially at the microscopic scale, which will directly affect the device performances at varying temperatures. Here, we map the contact potential difference and photocurrent distribution of MAPbI3 at different temperatures in situ by Kelvin probe force microscopy and conductive atomic force microscopy, emphasizing the different influences of variable temperature and phase transition on the photoelectric properties of grains and grain boundaries (GBs). It is discovered that both the Fermi level and photocurrent decrease as the sample is heated from 30 to 80 °C gradually because of the variation of effective carrier concentration and the degradation of carrier mobility implicated by lattice vibration scattering. The difference between the Fermi level at GBs and that on the grains ascends first and then descends, peaking at 50 °C, near which MAPbI3 transforms from a tetragonal phase to a cubic phase. This peak is speculated as a comprehensive consequence of the increasing difference of the Fermi level of semiconductors with different doping concentrations and the converging properties of grains and GBs with the temperature rising because the lower ion activation energy of the cubic phase at higher temperatures facilitates greatly the ions' movement between grains and GB. The variation trend of the difference of the photocurrent is the same. These findings advance the knowledge on the temperature-induced variations of microscopic photoelectrical properties of organic-inorganic hybrid perovskite materials, which may guide the development of strategies for improving their thermal stability.

Substrate Metabolism-Driven Assembly of High-Quality CdS xSe1- x Quantum Dots in Escherichia coli: Molecular Mechanisms and Bioimaging Application.

Biosynthesis offers opportunities for cost-effective and sustainable production of semiconductor quantum dots (QDs), but is currently restricted by poor controllability on the synthesis process, resulting from limited knowledge on the assembly mechanisms and the lack of effective control strategies. In this work, we provide molecular-level insights into the formation mechanism of biogenic QDs (Bio-QDs) and its connection with the cellular substrate metabolism in Escherichia coli. Strengthening the substrate metabolism for producing more reducing power was found to stimulate the production of several reduced thiol-containing proteins (including glutaredoxin and thioredoxin) that play key roles in Bio-QDs assembly. This effectively diverted the transformation route of the selenium (Se) and cadmium (Cd) metabolic from Cd3(PO4)2 formation to CdS xSe1- x QDs assembly, yielding fine-sized (2.0 ± 0.4 nm), high-quality Bio-QDs with quantum yield (5.2%) and fluorescence lifetime (99.19 ns) far exceeding the existing counterparts. The underlying mechanisms of Bio-QDs crystallization and development were elucidated by density functional theory calculations and molecular dynamics simulation. The resulting Bio-QDs were successfully used for bioimaging of cancer cells and tumor tissue of mice without extra modification. Our work provides fundamental knowledge on the Bio-QDs assembly mechanisms and proposes an effective, facile regulation strategy, which may inspire advances in controlled synthesis and practical applications of Bio-QDs as well as other bionanomaterials.

Selenium Stimulates Cadmium Detoxification in Caenorhabditis elegans through Thiols-Mediated Nanoparticles Formation and Secretion.

Antagonism between heavy metal and selenium (Se) could significantly affect their biotoxicity, but little is known about the mechanisms underlying such microbial-mediated antagonistic processes as well as the formed products. In this work, we examined the cadmium (Cd)-Se interactions and their fates in Caenorhabditis elegans through in vivo and in vitro analysis and elucidated the machinery of Se-stimulated Cd detoxification. Although the Se introduction induced up to 3-fold higher bioaccumulation of Cd in C. elegans than the Cd-only group, the nematode viability remained at a similar level to the Cd-only group. The relatively lower level of reactive oxygen species in the Se & Cd group confirms a significantly enhanced Cd detoxification by Se. The Cd-Se interaction, mediated by multiple thiols, including glutathione and phytochelatin, resulted in the formation of less toxic cadmium selenide (CdSe)/cadmium sulfide (CdS) nanoparticles. The CdSe/CdS nanoparticles were mainly distributed in the pharynx and intestine of the nematodes, and continuously excreted from the body, which also benefitted the C. elegans survival. Our findings shed new light on the microbial-mediated Cd-Se interactions and may facilitate an improved understanding and control of Cd biotoxicity in complicated coexposure environments.

-60 °C solution synthesis of atomically dispersed cobalt electrocatalyst with superior performance.

Temperature can govern morphologies, structures and properties of products from synthesis in solution. A reaction in solution at low temperature may result in different materials than at higher temperature due to thermodynamics and kinetics of nuclei formation. Here, we report a low-temperature solution synthesis of atomically dispersed cobalt in a catalyst with superior performance. By using a water/alcohol mixed solvent with low freezing point, liquid-phase reduction of a cobalt precursor with hydrazine hydrate is realized at -60 °C. A higher energy barrier and a sluggish nucleation rate are achieved to suppress nuclei formation; thus atomically dispersed cobalt is successfully obtained in a catalyst for oxygen reduction with electrochemical performance superior to that of a Pt/C catalyst. Furthermore, the atomically dispersed cobalt catalyst is applied in a microbial fuel cell to obtain a high maximum power density (2550 ± 60 mW m-2) and no current drop upon operation for 820 h.

Biogenic Quantum Dots for Sensitive, Label-Free Detection of Mercury Ions.

Nanoparticle-based fluorescent probes, typically fabricated by a chemical synthesis route, have been widely used for monitoring trace heavy metals in environments. However, the high-cost and complicated, aggressive fabrication processes restrict their widespread application. In this work, we report the first use of biogenic quantum dots (Bio-QDs) as a highly sensitive, low-cost fluorescent probe for label-free detection of mercury ions (Hg2+), with comparable performance to conventional chemically synthesized counterparts. Fluorescent Bio-QDs with uniform sizes (1.6 ± 0.3 nm) and unique core-shell structure (CdSxSe1-x core and protein- and phosphate-rich capping) were assembled by Escherichia coli cells. The Bio-QDs were extracted and directly used as a Hg2+ probe, which exhibited sensitive, linear fluorescent response to Hg2+ concentration in the range of 1.5-100 nM. Interestingly, it even enable a naked-eye detection of Hg2+ in a higher concentration range of 0.1-10 µM by simply raising the Bio-QD load. The underlying detection mechanisms, involving substitution of the Cd atoms with Hg from water, were revealed by Raman spectra, X-ray absorption fine structure, and density functional theory calculations. Our work implies a high potential of green-synthesized Bio-QDs for environmental monitoring applications, which may not only broaden the application ranges of Bio-QDs, but also advance the development of environmental analytical techniques toward higher sustainability.

Thermodynamically Stable Orthorhombic γ-CsPbI3 Thin Films for High-Performance Photovoltaics.

All-inorganic lead halide perovskites demonstrate improved thermal stability over the organic-inorganic halide perovskites, but the cubic α-CsPbI3 with the most appropriate bandgap for light harvesting is not structurally stable at room temperature and spontaneously transforms into the undesired orthorhombic δ-CsPbI3. Here, we present a new member of black-phase thin films of all-inorganic perovskites for high-efficiency photovoltaics, the orthorhombic γ-CsPbI3 thin films with intrinsic thermodynamic stability and ideal electronic structure. Exempt from introducing organic ligands or incorporating mixed cations/anions into the crystal lattice, we stabilize the γ-CsPbI3 thin films by a simple solution process in which a small amount of H2O manipulates the size-dependent phase formation through a proton transfer reaction. Theoretical calculations coupled with experiments show that γ-CsPbI3 with a lower surface free energy becomes thermodynamically preferred over δ-CsPbI3 at surface areas greater than 8600 m2/mol and exhibits comparable optoelectronic properties to α-CsPbI3. Consequently, γ-CsPbI3-based solar cells display a highly reproducible efficiency of 11.3%, among the highest records for CsPbI3 thin-film solar cells, with robust stability in ambient atmosphere for months and continuous operating conditions for hours. Our study provides a novel and fundamental perspective to overcome the Achilles' heel of the inorganic lead iodide perovskite and opens it up for high-performance optoelectronic devices.

Polar Solvent Induced Lattice Distortion of Cubic CsPbI3 Nanocubes and Hierarchical Self-Assembly into Orthorhombic Single-Crystalline Nanowires.

Despite the recent surge of interest in inorganic lead halide perovskite nanocrystals, there are still significant gaps in their stability disturbance and the understanding of their destabilization, assembly, and growth processes. Here, we discover that polar solvent molecules can induce the lattice distortion of ligand-stabilized cubic CsPbI3, leading to the phase transition into orthorhombic phase, which is unfavorable for photovoltaic applications. Such lattice distortion triggers the dipole moment on CsPbI3 nanocubes, which subsequently initiates the hierarchical self-assembly of CsPbI3 nanocubes into single-crystalline nanowires. The systematic investigations and in situ monitoring on the kinetics of the self-assembly process disclose that the more amount or the stronger polarity of solvent can induce the more rapid self-assembly and phase transition. These results not only elucidate the destabilization mechanism of cubic CsPbI3 nanocrystals, but also open up opportunities to synthesize and store cubic CsPbI3 for their practical applications in photovoltaics and optoelectronics.

A Two-Dimensional Hole-Transporting Material for High-Performance Perovskite Solar Cells with 20 % Average Efficiency.

A readily available small molecular hole-transporting material (HTM), OMe-TATPyr, was synthesized and tested in perovskite solar cells (PSCs). OMe-TATPyr is a two-dimensional π-conjugated molecule with a pyrene core and four phenyl-thiophene bridged triarylamine groups. It can be readily synthesized in gram scale with a low lab cost of around US$ 50 g-1 . The incorporation of the phenyl-thiophene units in OMe-TATPyr are beneficial for not only carrier transportation through improved charge delocalization and intermolecular stacking, but also potential trap passivation via Pb-S interaction as supported by depth-profiling XPS, photoluminescence, and electrochemical impedance analysis. As a result, an impressive best power conversion efficiency (PCE) of up to 20.6 % and an average PCE of 20.0 % with good stability has been achieved for mixed-cation PSCs with OMe-TATPyr with an area of 0.09 cm2 . A device with an area of 1.08 cm2 based on OMe-TATPyr demonstrates a PCE of 17.3 %.

Mitigating Interfacial Potential Drop of Cathode-Solid Electrolyte via Ionic Conductor Layer To Enhance Interface Dynamics for Solid Batteries.

The rapid capacity decay caused by the poor contact and large polarization at the interface between the cathode and solid electrolytes is still a big challenge to overcome for high-power-density solid batteries. In this study, a superior Li+ conductive transition layer Li1.4Al0.4Ti1.6(PO4)3 is introduced to coat LiNi0.6Co0.2Mn0.2O2, as a model cathode, to mitigate polarization and enhance dynamic characteristics. The critical attribute for such superior dynamics is investigated by the atomic force microscopy with boundary potential analysis, revealing that the formed interfacial transition layer provides a gradual potential slope and sustain-released polarization, and endows the battery with improved cycling stability (90% after 100 cycles) and excellent rate capability (116 mA h g-1 at 2 C) at room temperature, which enlightens the comprehension of interface engineering in the future solid batteries systems.

Spectral insights into the transformation and distribution of CdSe quantum dots in microorganisms during food-chain transport.

The discharge of engineered nanomaterials (ENMs) into environment is raising widespread concern not only due to their direction bio-toxicity but also their bio-concentration and bio-magnification through food web. However, the transformation and distribution of ENMs during food-chain transport are poorly understood, due to lack of accurate, reliable analytical methods. In this study, by using a suite of advanced spectrum techniques, we successfully tracked the distribution and biotransformation dynamics of CdSe quantum dots (QDs) during their transport from Shewanella onedensis to Caenorchabditis elegans in predation. Fluorescence microscopy and Raman mapping showed that the ingested QDs by C. elegans were located at the gut lumen and subcutaneous tissue, and were partially excreted from the nematode body over time. Micro-X-ray fluorescence (µ-XRF) spectroscopy and Se K-edge X-ray absorption fine structure (XAFS) results further revealed the changed distribution of Se element over time, and a shift in the major Se species from CdSe to Se0 and Na2SeO3IV. This work demonstrates the utility of advanced spectral techniques for characterizing QDs in vivo, and may facilitate a better understanding on the environmental transformation and fates of ENMs.

Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis.

Compressive surface strains have been necessary to boost oxygen reduction reaction (ORR) activity in core/shell M/platinum (Pt) catalysts (where M can be nickel, cobalt, or iron). We report on a class of platinum-lead/platinum (PtPb/Pt) core/shell nanoplate catalysts that exhibit large biaxial strains. The stable Pt (110) facets of the nanoplates have high ORR specific and mass activities that reach 7.8 milliampere (mA) per centimeter squared and 4.3 ampere per milligram of platinum at 0.9 volts versus the reversible hydrogen electrode (RHE), respectively. Density functional theory calculations reveal that the edge-Pt and top (bottom)-Pt (110) facets undergo large tensile strains that help optimize the Pt-O bond strength. The intermetallic core and uniform four layers of Pt shell of the PtPb/Pt nanoplates appear to underlie the high endurance of these catalysts, which can undergo 50,000 voltage cycles with negligible activity decay and no apparent structure and composition changes.

General Space-Confined On-Substrate Fabrication of Thickness-Adjustable Hybrid Perovskite Single-Crystalline Thin Films.

Organic-inorganic hybrid perovskite single-crystalline thin films (SCTFs) are promising for enhancing photoelectric device performance due to high carrier mobility, long diffusion length, and carrier lifetime. However, bulk perovskite single crystals available today are not suitable for practical device application due to the unfavorable thickness. Herein, we report a facile space-confined solution-processed strategy to on-substrate grow various hybrid perovskite SCTFs in a size of submillimeter with adjustable thicknesses from nano- to micrometers. These SCTFs exhibit photoelectric properties comparable to bulk single crystals with low defect density and good air stability. The clear thickness-dependent colors allow fast visual selection of SCTFs with a suitable thickness for specific device application. The present substrate-independent growth of perovskite SCTFs opens up opportunities for on-chip fabrication of diverse high-performance devices.

Tuning the Fermi-level of TiO2 mesoporous layer by lanthanum doping towards efficient perovskite solar cells.

Tuning the band alignment is proved to be an effective way to facilitate carrier transportation and thus enhance the power conversion efficiency (PCE) of solar cells. Doping the compact layer with metal ions or modifying the interfaces among functional layers in perovskite solar cells (PSCs) can appreciably improve the PCE of PSCs. Inspired by the rare earth elemental doping of TiO2, which has witnessed the success in photocatalysis and dye-sensitized solar cells, we firstly demonstrated here that La3+ doping in the mesoporous TiO2 layer of a mesostructured PSC can tune its Fermi level and thus significantly enhance the device PCE. Systematic analysis reveals that doping La3+ into TiO2 raises the Fermi level of TiO2 through scavenging oxygen and inducing vacancies, which subsequently increases the open circuit voltage and the fill factor while reducing the series resistance of the PSC using La3+-doped TiO2 as a mesoporous layer. As a result, a PCE of 15.42% is achieved, which is appreciably higher than the PCE of a device with undoped TiO2 (12.11%).

Influence of N,N-Dimethylformamide Annealing on the Local Electrical Properties of Organometal Halide Perovskite Solar Cells: an Atomic Force Microscopy Investigation.

Organometal halide perovskites have been recognized as a new class of materials for photovoltaic application. Solvent annealing introduced during crystallization of bulk or thin-film materials can improve the performance of perovskite solar cells. Herein, we present Kelvin probe force microscopy and conductive atomic force microscopy (c-AFM) measurements to investigate the local optoelectronic properties of a perovskite film after N,N-dimethylformamide (DMF) annealing. AFM results show that DMF annealing induces recrystallization, yielding a large-size polycrystalline perovskite film. Uniform and higher photocurrent is distributed on the film. However, lower surface potential enhancement and photocurrent are observed at grain boundaries (GBs), illustrating that GBs acting as recombination sites are detrimental to photocurrent transport and collection. Our observation provides a nanoscale understanding of the device performance improvement after DMF annealing.

Solvent-Assisted Preparation of High-Performance Mesoporous CH3NH3Pbl3 Perovskite Solar Cells.

Organometal trihalide perovskite based solar cells have attracted great attention worldwide since their power conversion efficiency (PCE) have risen to over 15% within only 3 years of development. Comparing with other types of perovskite solar cells, mesostructured perovskite solar cells based on CH3NH3Pbl3 as light harvesting material have already demonstrated remarkable advance in performance and reproducibility. Here, we reported a mesoscopic TiO2/CH3NH3Pbl3 heterojunction solar cell with uniform perovskite thin film prepared via solvent-assisted solution processing method. The best performing device delivered photocurrent density of 20.11 mA cm⁻², open-circuit voltage of 1.02 V, and fill factor of 0.70, leading to a PCE of 14.41%. A small anomalous hysteresis in the J-V curves was observed, where the PCE at forward scan was measured to be 84% of the PCE at reverse scan. Based on a statistical analysis, the perovskite solar cells prepared by the reported method exhibited reproducible and high PCE, indicating its promising application in the fabrication of low-cost and high-efficiency perovskite solar cells.

Microscopic Investigation of Grain Boundaries in Organolead Halide Perovskite Solar Cells.

Grain boundaries (GBs) play an important role in organic-inorganic halide perovskite solar cells, which have generally been recognized as a new class of materials for photovoltaic applications. To definitely understand the electrical structure and behavior of GBs, here we present Kelvin probe force microscopy and conductive atomic force microscopy (c-AFM) measurements of both typical and inverted planar organolead halide perovskite solar cells. By comparing the contact potential difference (CPD) of these two devices in the dark and under illumination, we found that a downward band bending exists in GBs that predominantly attract photoinduced electrons. The c-AFM measurements observed that higher photocurrents flow through GBs when a low bias overcomes the barrier created by the band bending, indicating that GBs act as effective charge dissociation interfaces and photocurrent transduction pathways rather than recombination sites.