Gate Controlled Excitonic Emission in Quantum Dot Thin Films.

Formation of charged trions is detrimental to the luminescence quantum efficiency of colloidal quantum dot (QD) thin films as they predominantly undergo nonradiative recombination. In this regard, control of charged trion formation is of interest for both fundamental characterization of the quasi-particles and performance optimization. Using CdSe/CdS QDs as a prototypical material system, here we demonstrate a metal-oxide-semiconductor capacitor based on QD thin films for studying the background charge effect on the luminescence efficiency and lifetime. The concentration ratio of the charged and neutral quasiparticles in the QDs is reversibly controlled by applying a gate voltage, while simultaneous steady-state and time-resolved photoluminescence measurements are performed. Notably, the photoluminescence intensity is modulated by up to 2 orders of magnitude with a corresponding change in the effective lifetime. In addition, chip-scale modulation of brightness is demonstrated, where the photoluminescence is effectively turned on and off by the gate, highlighting potential applications in voltage-controlled electrochromics.

Effect of Feature Shape and Dimension of a Confinement Geometry on Selectivity of Electrocatalytic CO2 Reduction.

The local confinement effect, which can generate a high concentration of hydroxide ions and reaction intermediates near the catalyst surface, is an important strategy for converting CO2 into multi-carbon products in electrocatalytic CO2 reduction. Therefore, understanding how the shape and dimension of the confinement geometry affect the product selectivity is crucial. In this study, we report for the first time the effect of the shape (degree of confinement) and dimension of the confined space on the product selectivity without changing the intrinsic property of Cu. We demonstrate that geometry influences the outcomes of products, such as CH4 , C2 H4 , and EtOH, in different ways: the selectivity of CH4 and EtOH is affected by shape, while the selectivity of C2 H4 is influenced by dimension of geometry predominantly. These phenomena are demonstrated, both experimentally and through simulation, to be induced by the local confinement effect within the confined structure. Our geometry model could serve as basis for designing the confined structures tailored for the production of specific products.

Selective and Stable CO2 Electroreduction to CH4 via Electronic Metal-Support Interaction upon Decomposition/Redeposition of MOF.

The CO2 electroreduction to fuels is a feasible approach to provide renewable energy sources. Therefore, it is necessary to conduct experimental and theoretical investigations on various catalyst design strategies, such as electronic metal-support interaction, to improve the catalytic selectivity. Here a solvent-free synthesis method is reported to prepare a copper (Cu)-based metal-organic framework (MOF) as the precursor. Upon electrochemical CO2 reduction in aqueous electrolyte, it undergoes in situ decomposition/redeposition processes to form abundant interfaces between Cu nanoparticles and amorphous carbon supports. This Cu/C catalyst favors the selective and stable production of CH4 with a Faradaic efficiency of ≈55% at -1.4 V versus reversible hydrogen electrode (RHE) for 12.5 h. The density functional theory calculation reveals the crucial role of interfacial sites between Cu and amorphous carbon support in stabilizing the key intermediates for CO2 reduction to CH4 . The adsorption of COOH* and CHO* at the Cu/C interface is up to 0.86 eV stronger than that on Cu(111), thus promoting the formation of CH4 . Therefore, it is envisioned that the strategy of regulating electronic metal-support interaction can improve the selectivity and stability of catalyst toward a specific product upon electrochemical CO2 reduction.

Giant Isotope Effect of Thermal Conductivity in Silicon Nanowires.

Isotopically purified semiconductors potentially dissipate heat better than their natural, isotopically mixed counterparts as they have higher thermal conductivity (κ). But the benefit is low for Si at room temperature, amounting to only ∼10% higher κ for bulk ^{28}Si than for bulk natural Si (^{nat}Si). We show that in stark contrast to this bulk behavior, ^{28}Si (99.92% enriched) nanowires have up to 150% higher κ than ^{nat}Si nanowires with similar diameters and surface morphology. Using a first-principles phonon dispersion model, this giant isotope effect is attributed to a mutual enhancement of isotope scattering and surface scattering of phonons in ^{nat}Si nanowires, correlated via transmission of phonons to the native amorphous SiO_{2} shell. The Letter discovers the strongest isotope effect of κ at room temperature among all materials reported to date and inspires potential applications of isotopically enriched semiconductors in microelectronics.

Wetting-regulated gas-involving (photo)electrocatalysis: biomimetics in energy conversion.

(Photo)electrolysis of water or gases with water to species serving as industrial feedstocks and energy carriers, such as hydrogen, ammonia, ethylene, propanol, etc., has drawn tremendous attention. Moreover, these processes can often be driven by renewable energy under ambient conditions as a sustainable alternative to traditional high-temperature and high-pressure synthesis methods. In addition to the extensive studies on catalyst development, increasing attention has been paid to the regulation of gas transport/diffusion behaviors during gas-involving (photo)electrocatalytic reactions towards the goal of creating industrially viable catalytic systems with high reaction rates, excellent long-term stabilities and near-unity selectivities. Biomimetic surfaces and systems with special wetting capabilities and structural advantages can shed light on the future design of (photo)electrodes and address long-standing challenges. This article is dedicated to bridging the fields of wetting and catalysis by reviewing the cutting-edge design methodologies of both gas-evolving and gas-consuming (photo)electrocatalytic systems. We first introduce the fundamentals of various in-air/underwater wetting states and their corresponding bioinspired structural properties. The relationship amongst the bubble transport behavior, wettability, and porosity/tortuosity is also discussed. Next, the latest implementations of wetting-related design principles for gas-evolving reactions (i.e. the hydrogen evolution reaction and oxygen evolution reaction) and gas-consuming reactions (i.e. the oxygen reduction reaction and CO2 reduction reaction) are summarized. For photoelectrode designs, additional factors are taken into account, such as light absorption and the separation, transport and recombination of photoinduced electrons and holes. The influences of wettability and 3D structuring of (photo)electrodes on the catalytic activity, stability and selectivity are analyzed to reveal the underlying mechanisms. Finally, remaining questions and related future perspectives are outlined.

Effects of surface diffusion in electrocatalytic CO2 reduction on Cu revealed by kinetic Monte Carlo simulations.

Kinetic Monte Carlo (KMC) methods are frequently used for mechanistic studies of thermally driven heterogeneous catalysis systems but are underused for electrocatalysis. Here, we develop a lattice KMC approach for electrocatalytic CO2 reduction. The work is motivated by a prior experimental report that performed electroreduction of a mixed feed of 12CO2 and 13CO on Cu; differences in the 13C content of C2 products ethylene and ethanol (Δ13C) were interpreted as evidence of site selectivity. The lattice KMC model considers the effect of surface diffusion on this system. In the limit of infinitely fast diffusion (mean-field approximation), the key intermediates 12CO* and 13CO* would be well mixed on the surface and no evidence of site selectivity could have been observed. Using a simple two-site model and adapting a previously reported microkinetic model, we assess the effects of diffusion on the relative isotope fractions in the products using the estimated surface diffusion rate of CO* from literature reports. We find that the size of the active sites and the total surface adsorbate coverage can have a large influence on the values of Δ13C that can be observed. Δ13C is less sensitive to the CO* diffusion rate as long as it is within the estimated range. We further offer possible methods to estimate surface distribution of intermediates and to predict intrinsic selectivity of active sites based on experimental observations. This work illustrates the importance of considering surface diffusion in the study of electrochemical CO2 reduction to multi-carbon products. Our approach is entirely based on a freely available open-source code, so will be readily adaptable to other electrocatalytic systems.

Surface Composition Dependent Ligand Effect in Tuning the Activity of Nickel-Copper Bimetallic Electrocatalysts toward Hydrogen Evolution in Alkaline.

Exploring efficient and low-cost electrocatalysts for hydrogen evolution reaction (HER) in alkaline media is critical for developing anion exchange membrane electrolyzers. The key to a rational catalyst design is understanding the descriptors that govern the alkaline HER activity. Unfortunately, the principles that govern the alkaline HER performance remain unclear and are still under debate. By studying the alkaline HER at a series of NiCu bimetallic surfaces, where the electronic structure is modulated by the ligand effect, we demonstrate that alkaline HER activity can be correlated with either the calculated or the experimental-measured d band center (an indicator of hydrogen binding energy) via a volcano-type relationship. Such correlation indicates the descriptor role of the d band center, and this hypothesis is further supported by the evidence that combining Ni and Cu produces a variety of adsorption sites, which possess near-optimal hydrogen binding energy. Our finding broadens the applicability of d band theory to activity prediction of metal electrocatalysts and may offer an insightful understanding of alkaline HER mechanism.

Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products.

Numerous studies have examined the electrochemical reduction of CO (COR) to oxygenates (e.g., ethanol). None have considered the possibility that oxygen in the product might arise from water rather than from CO. To test this assumption, C16O reduction was performed in H218O electrolyte. Surprisingly, we found that 60-70% of the ethanol contained 18O, which must have originated from the solvent. We extended our previous all-solvent density functional theory metadynamics calculations to consider the possibility of incorporating water, and indeed, we found a new mechanism involving a Grotthuss chain of six water molecules in a concerted reaction with the *C-CH intermediate to form *CH-CH(18OH), subsequently leading to (18O)ethanol. This competes with the formation of ethylene that also arises from *C-CH. These unforeseen results suggest that all previous studies of COR under aqueous conditions must be reexamined.

Measuring the Edge Recombination Velocity of Monolayer Semiconductors.

Understanding edge effects and quantifying their impact on the carrier properties of two-dimensional (2D) semiconductors is an essential step toward utilizing this material for high performance electronic and optoelectronic devices. WS2 monolayers patterned into disks of varying diameters are used to experimentally explore the influence of edges on the material's optical properties. Carrier lifetime measurements show a decrease in the effective lifetime, τeffective, as a function of decreasing diameter, suggesting that the edges are active sites for carrier recombination. Accordingly, we introduce a metric called edge recombination velocity (ERV) to characterize the impact of 2D material edges on nonradiative carrier recombination. The unpassivated WS2 monolayer disks yield an ERV ∼ 4 × 104 cm/s. This work quantifies the nonradiative recombination edge effects in monolayer semiconductors, while simultaneously establishing a practical characterization approach that can be used to experimentally explore edge passivation methods for 2D materials.

Pressure-Temperature Phase Diagram of Vanadium Dioxide.

The complexity of strongly correlated electron physics in vanadium dioxide is exemplified as its rich phase diagrams of all kinds, which in turn shed light on the mechanisms behind its various phase transitions. In this work, we map out the hydrostatic pressure-temperature phase diagram of vanadium dioxide nanobeams by independently varying pressure and temperature with a diamond anvil cell. In addition to the well-known insulating M1 (monoclinic) and metallic R (tetragonal) phases, the diagram identifies the existence at high pressures of the insulating M1' (monoclinic, more conductive than M1) phase and two metallic phases of X (monoclinic) and O (orthorhombic, at high temperature only). Systematic optical and electrical measurements combined with density functional calculations allow us to delineate their phase boundaries as well as reveal some basic features of the transitions.

Pressurizing Field-Effect Transistors of Few-Layer MoS2 in a Diamond Anvil Cell.

Hydrostatic pressure applied using diamond anvil cells (DAC) has been widely explored to modulate physical properties of materials by tuning their lattice degree of freedom. Independently, electrical field is able to tune the electronic degree of freedom of functional materials via, for example, the field-effect transistor (FET) configuration. Combining these two orthogonal approaches would allow discovery of new physical properties and phases going beyond the known phase space. Such experiments are, however, technically challenging and have not been demonstrated. Herein, we report a feasible strategy to prepare and measure FETs in a DAC by lithographically patterning the nanodevices onto the diamond culet. Multiple-terminal FETs were fabricated in the DAC using few-layer MoS2 and BN as the channel semiconductor and dielectric layer, respectively. It is found that the mobility, conductance, carrier concentration, and contact conductance of MoS2 can all be significantly enhanced with pressure. We expect that the approach could enable unprecedented ways to explore new phases and properties of materials under coupled mechano-electrostatic modulation.

Quantifying van der Waals Interactions in Layered Transition Metal Dichalcogenides from Pressure-Enhanced Valence Band Splitting.

van der Waals (vdW) forces, despite being relatively weak, hold the layers together in transition metal dichalcogenides (TMDs) and play a key role in their band structure evolution, hence profoundly affecting their physical properties. In this work, we experimentally probe the vdW interactions in MoS2 and other TMDs by measuring the valence band maximum (VBM) splitting (Δ) at K point as a function of pressure in a diamond anvil cell. As high pressure increases interlayer wave function coupling, the VBM splitting is enhanced in 2H-stacked MoS2 multilayers but, due to its specific geometry, not in 3R-stacked multilayers, hence allowing the interlayer contribution to be separated out of the total VBM splitting, as well as predicting a negative pressure (2.4 GPa) where the interlayer contribution vanishes. This negative pressure represents the threshold vdW interaction beyond which neighboring layers are electronically decoupled. This approach is compared to first-principles calculations and found to be widely applicable to other group-VI TMDs.

Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18 O Labeling.

Oxide-derived (OD) Cu catalysts have high selectivity towards the formation of multi-carbon products (C2 /C3 ) for aqueous electrochemical CO2 reduction (CO2 R). It has been proposed that a large fraction of the initial oxide can be surprisingly resistant to reduction, and these residual oxides play a crucial catalytic role. The stability of residual oxides was investigated by synthesizing 18 O-enriched OD Cu catalysts and testing them for CO2 R. These catalysts maintain a high selectivity towards C2 /C3 products (ca. 60 %) for up to 5 h in 0.1 m KHCO3 at -1.0 V vs. RHE. However, secondary-ion mass spectrometry measurements show that only a small fraction (<1 %) of the original 18 O content remains, showing that residual oxides are not present in significant amounts during CO2 R. Furthermore, we show that OD Cu can reoxidize rapidly, which could compromise the accuracy of ex situ methods for determining the true oxygen content.

Al(2)O(3) Surface Complexation for Photocatalytic Organic Transformations.

The use of sunlight to drive organic reactions constitutes a green and sustainable strategy for organic synthesis. Herein, we discovered that the earth-abundant aluminum oxide (Al2O3) though paradigmatically known to be an insulator could induce an immense increase in the selective photo-oxidation of different benzyl alcohols in the presence of a large variety of dyes and O2. This unique phenomenon is based on the surface complexation of benzyl alcohol (BnOH) with the Brønsted base sites on Al2O3, which reduces its oxidation potential and causes an upshift in its HOMO for electron abstraction by the dye. The surface complexation of O2 with Al2O3 also activates the adsorbed O2 for receiving electrons from the photoexcited dyes. This discovery brings forth a new understanding on utilizing surface complexation mechanisms between the reactants and earth abundant materials to effectively achieve a wider range of photoredox reactions.

High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites.

Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH3NH3PbI3-xBrx perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ Eg ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells.

Recombination Kinetics and Effects of Superacid Treatment in Sulfur- and Selenium-Based Transition Metal Dichalcogenides.

Optoelectronic devices based on two-dimensional (2D) materials have shown tremendous promise over the past few years; however, there are still numerous challenges that need to be overcome to enable their application in devices. These include improving their poor photoluminescence (PL) quantum yield (QY) as well as better understanding of exciton-based recombination kinetics. Recently, we developed a chemical treatment technique using an organic superacid, bis(trifluoromethane)sulfonimide (TFSI), which was shown to improve the quantum yield in MoS2 from less than 1% to over 95%. Here, we perform detailed steady-state and transient optical characterization on some of the most heavily studied direct bandgap 2D materials, specifically WS2, MoS2, WSe2, and MoSe2, over a large pump dynamic range to study the recombination mechanisms present in these materials. We then explore the effects of TFSI treatment on the PL QY and recombination kinetics for each case. Our results suggest that sulfur-based 2D materials are amenable to repair/passivation by TFSI, while the mechanism is thus far ineffective on selenium based systems. We also show that biexcitonic recombination is the dominant nonradiative pathway in these materials and that the kinetics for TFSI treated MoS2 and WS2 can be described using a simple two parameter model.

General Thermal Texturization Process of MoS2 for Efficient Electrocatalytic Hydrogen Evolution Reaction.

Molybdenum disulfide (MoS2) has been widely examined as a catalyst containing no precious metals for the hydrogen evolution reaction (HER); however, these examinations have utilized synthesized MoS2 because the pristine MoS2 mineral is known to be a poor catalyst. The fundamental challenge with pristine MoS2 is the inert HER activity of the predominant (0001) basal surface plane. In order to achieve high HER performance with pristine MoS2, it is essential to activate the basal plane. Here, we report a general thermal process in which the basal plane is texturized to increase the density of HER-active edge sites. This texturization is achieved through a simple thermal annealing procedure in a hydrogen environment, removing sulfur from the MoS2 surface to form edge sites. As a result, the process generates high HER catalytic performance in pristine MoS2 across various morphologies such as the bulk mineral, films composed of micron-scale flakes, and even films of a commercially available spray of nanoflake MoS2. The lowest overpotential (η) observed for these samples was η = 170 mV to obtain 10 mA/cm(2) of HER current density.

Chemical Bath Deposition of p-Type Transparent, Highly Conducting (CuS)x:(ZnS)1-x Nanocomposite Thin Films and Fabrication of Si Heterojunction Solar Cells.

P-type transparent conducting films of nanocrystalline (CuS)x:(ZnS)1-x were synthesized by facile and low-cost chemical bath deposition. Wide angle X-ray scattering (WAXS) and high resolution transmission electron microscopy (HRTEM) were used to evaluate the nanocomposite structure, which consists of sub-5 nm crystallites of sphalerite ZnS and covellite CuS. Film transparency can be controlled by tuning the size of the nanocrystallites, which is achieved by adjusting the concentration of the complexing agent during growth; optimal films have optical transmission above 70% in the visible range of the spectrum. The hole conductivity increases with the fraction of the covellite phase and can be as high as 1000 S cm(-1), which is higher than most reported p-type transparent materials and approaches that of n-type transparent materials such as indium tin oxide (ITO) and aluminum doped zinc oxide (AZO) synthesized at a similar temperature. Heterojunction p-(CuS)x:(ZnS)1-x/n-Si solar cells were fabricated with the nanocomposite film serving as a hole-selective contact. Under 1 sun illumination, an open circuit voltage of 535 mV was observed. This value compares favorably to other emerging heterojunction Si solar cells which use a low temperature process to fabricate the contact, such as single-walled carbon nanotube/Si (370-530 mV) and graphene/Si (360-552 mV).

Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu.

Electrolyte cation size is known to influence the electrochemical reduction of CO2 over metals; however, a satisfactory explanation for this phenomenon has not been developed. We report here that these effects can be attributed to a previously unrecognized consequence of cation hydrolysis occurring in the vicinity of the cathode. With increasing cation size, the pKa for cation hydrolysis decreases and is sufficiently low for hydrated K+, Rb+, and Cs+ to serve as buffering agents. Buffering lowers the pH near the cathode, leading to an increase in the local concentration of dissolved CO2. The consequences of these changes are an increase in cathode activity, a decrease in Faradaic efficiencies for H2 and CH4, and an increase in Faradaic efficiencies for CO, C2H4, and C2H5OH, in full agreement with experimental observations for CO2 reduction over Ag and Cu.

Effects of temperature and gas-liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO2 reduction electrocatalysts.

In the last few years, there has been increased interest in electrochemical CO2 reduction (CO2R). Many experimental studies employ a membrane separated, electrochemical cell with a mini H-cell geometry to characterize CO2R catalysts in aqueous solution. This type of electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. We show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences due to the complexity of the physical phenomena taking place on electrode surfaces during CO2R, particularly as they relate to the cell temperature and bulk electrolyte CO2 concentration. Both effects were evaluated quantitatively in high S/V cells using Cu electrodes and a bicarbonate buffer electrolyte. Electrolyte temperature is a function of the current/total voltage passed through the cell and the cell geometry. Even at a very high current density, 20 mA cm-2, the temperature increase was less than 4 °C and a decrease of <10% in the dissolved CO2 concentration is predicted. In contrast, limits on the CO2 gas-liquid mass transfer into the cells produce much larger effects. By using the pH in the cell to measure the CO2 concentration, significant undersaturation of CO2 is observed in the bulk electrolyte, even at more modest current densities of 10 mA cm-2. Undersaturation of CO2 produces large changes in the faradaic efficiency observed on Cu electrodes, with H2 production becoming increasingly favored. We show that the size of the CO2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO2 concentration in the electrolyte, and we have designed a high S/V cell that is able to maintain the near-equilibrium CO2 concentration at current densities up to 15 mA cm-2.