Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction

Carbon dioxide electroreduction in aqueous media using Cu catalysts can generate many different C2 and C3 products, which leads to the question whether all products are generated from the same types of active sites or if product-specific active sites are responsible for certain products. Here, by reducing mixtures of 13CO and 12CO2, we show that oxide-derived Cu catalysts have three different types of active sites for C–C coupled products, one that produces ethanol and acetate, another that produces ethylene and yet another that produces 1-propanol. In contrast, we do not find evidence of product-specific sites on polycrystalline Cu and oriented (100) and (111) Cu surfaces. Analysis of the isotopic composition of the products leads to the prediction that the adsorption energy of *COOH (the product of the first step of CO2 reduction) may be a descriptor for the product selectivity of a given active site. These new insights should enable highly selective catalysts to be developed

Machine Learning Optimization of p-Type Transparent Conducting Films

p-Type transparent conducting materials (p-TCMs) are important components of optoelectronic devices including solar cells, photodetectors, displays, and flexible sensors. Cu-Zn-S thin films prepared by chemical bath deposition (CBD) can have both high transparency in the visible range (>80%) as well as excellent hole conductivity (>1000 S cm-1). However, the interplay between the deposition parameters in the CBD process (metal and sulfur precursor concentrations, temperature, pH, complexing agents, etc.) creates a multidimensional parameter space such that optimization for a specific application is challenging and time-consuming. Here we show that strategic design of experiment combined with machine learning (ML) allows for the efficient optimization of p-TCM performance. The approach is guided by a figure of merit (FOM) calculated from the film conductivity and optical transmission in the desired spectral range. A specific example is shown using two steps of optimization using a selected subset of four experimental CBD factors. The ML model is based on support vector regression employing a radial basis function as the kernel function. 10-fold cross-validation was performed to mitigate overfitting. After the first round of optimization, predicted areas in the parameter space with maximal FOMs were selected for a second round of optimization. Films with optimal FOMs were incorporated into heterojunction solar cells and transparent photodiodes. The optimization approach shown here will be generally applicable to any materials synthesis process with multiple parameters

Si photocathode with Ag-supported dendritic Cu catalyst for CO2 reduction

Si photocathodes integrated with Ag-supported dendritic Cu catalysts are used to perform light-driven reduction of CO2 to C2 and C3 products in aqueous solution. A back illumination geometry with an n-type Si absorber was used to permit the use of absorbing metallic catalysts. Selective carrier collection was accomplished by a p+ implantation on the illumination side and an n+ implantation followed by atomic layer deposition of TiO2 on the electrolyte site. The Ag-supported dendritic Cu CO2 reduction catalyst was formed by evaporation of Ag followed by high-rate electrodeposition of Cu to form a high surface area structure. Under simulated 1 sun illumination in 0.1 M CsHCO3 saturated with CO2, the photovoltage generated by the Si (∼600 mV) enables C2 and C3 products to be produced at -0.4 vs. RHE. Texturing of both sides of the Si increases the light-limited current density, due to reduced reflection on the illumination side, and also deceases the onset potential. Under simulated diurnal illumination conditions photocathodes maintain over 60% faradaic efficiency to hydrocarbon and oxygenate products (mainly ethylene, ethanol, propanol) for several days. After 10 days of testing, contamination from the counter electrode is observed, which causes an increase in hydrogen production. This effect is mitigated by a regeneration procedure which restores the original catalyst selectivity. A tandem, self-powered CO2 reduction device was formed by coupling a Si photocathode with two series-connected semitransparent CH3NH3PbI3 perovskite solar cells, achieving an efficiency for the conversion of sunlight to hydrocarbons and oxygenates of 1.5% (3.5% for all products)

Compliant substrate epitaxy: Au on MoS2

A theory for the epitaxial growth of Au on MoS2 is developed and analyzed. The theory combines continuum linear elasticity theory with density functional theory to analyze epitaxial growth in this system. It is demonstrated that if one accounts for interfacial energies and strains, the presence of misfit dislocations, and the compliance of the MoS2 substrate, the experimentally observed growth orientation is favored despite the fact that it represents a larger elastic mismatch than two competing structures. The stability of the experimentally preferred orientation is attributed to the formation of a large number of strong Au-S bonds, and it is noted that this strong bond may serve as a means to exfoliate and transfer large single layers sheets of MoS2, as well as to engineer strain within single layers of MoS2. The potential for using a van der Waals-bonded layered material as a compliant substrate for applications in 2D electronic devices and epitaxial thin film growth is discussed

Line Broadening and Decoherence of Electron Spins in Phosphorus-Doped Silicon Due to Environmental 29^Si Nuclear Spins

Phosphorus-doped silicon single crystals with 0.19 % <= f <= 99.2 %, where f is the concentration of 29^Si isotopes, are measured at 8 K using a pulsed electron spin resonance technique, thereby the effect of environmental 29^Si nuclear spins on the donor electron spin is systematically studied. The linewidth as a function of f shows a good agreement with theoretical analysis. We also report the phase memory time T_M of the donor electron spin dependent on both f and the crystal axis relative to the external magnetic field.Comment: 5 pages, 4 figure

Immigrant community integration in world cities

As a consequence of the accelerated globalization process, today major cities all over the world are characterized by an increasing multiculturalism. The integration of immigrant communities may be affected by social polarization and spatial segregation. How are these dynamics evolving over time? To what extent the different policies launched to tackle these problems are working? These are critical questions traditionally addressed by studies based on surveys and census data. Such sources are safe to avoid spurious biases, but the data collection becomes an intensive and rather expensive work. Here, we conduct a comprehensive study on immigrant integration in 53 world cities by introducing an innovative approach: an analysis of the spatio-temporal communication patterns of immigrant and local communities based on language detection in Twitter and on novel metrics of spatial integration. We quantify the "Power of Integration" of cities --their capacity to spatially integrate diverse cultures-- and characterize the relations between different cultures when acting as hosts or immigrants.Comment: 13 pages, 5 figures + Appendi

Thermal Properties of Isotopically Engineered Graphene

In addition to its exotic electronic properties graphene exhibits unusually high intrinsic thermal conductivity. The physics of phonons - the main heat carriers in graphene - was shown to be substantially different in two-dimensional (2D) crystals, such as graphene, than in three-dimensional (3D) graphite. Here, we report our experimental study of the isotope effects on the thermal properties of graphene. Isotopically modified graphene containing various percentages of 13C were synthesized by chemical vapor deposition (CVD). The regions of different isotopic composition were parts of the same graphene sheet to ensure uniformity in material parameters. The thermal conductivity, K, of isotopically pure 12C (0.01% 13C) graphene determined by the optothermal Raman technique, was higher than 4000 W/mK at the measured temperature Tm~320 K, and more than a factor of two higher than the value of K in a graphene sheets composed of a 50%-50% mixture of 12C and 13C. The experimental data agree well with our molecular dynamics (MD) simulations, corrected for the long-wavelength phonon contributions via the Klemens model. The experimental results are expected to stimulate further studies aimed at better understanding of thermal phenomena in 2D crystals.Comment: 14 pages, 3 figure

Mineral maturity and crystallinity index are distinct characteristics of bone mineral

The purpose of this study was to test the hypothesis that mineral maturity and crystallinity index are two different characteristics of bone mineral. To this end, Fourier transform infrared microspectroscopy (FTIRM) was used. To test our hypothesis, synthetic apatites and human bone samples were used for the validation of the two parameters using FTIRM. Iliac crest samples from seven human controls and two with skeletal fluorosis were analyzed at the bone structural unit (BSU) level by FTIRM on sections 2–4 lm thick. Mineral maturity and crystallinity index were highly correlated in synthetic apatites but poorly correlated in normal human bone. In skeletal fluorosis, crystallinity index was increased and maturity decreased, supporting the fact of separate measurement of these two parameters. Moreover, results obtained in fluorosis suggested that mineral characteristics can be modified independently of bone remodeling. In conclusion, mineral maturity and crystallinity index are two different parameters measured separately by FTIRM and offering new perspectives to assess bone mineral traits in osteoporosis

Solid state quantum memory using the 31P nuclear spin

The transfer of information between different physical forms is a central theme in communication and computation, for example between processing entities and memory. Nowhere is this more crucial than in quantum computation, where great effort must be taken to protect the integrity of a fragile quantum bit. Nuclear spins are known to benefit from long coherence times compared to electron spins, but are slow to manipulate and suffer from weak thermal polarisation. A powerful model for quantum computation is thus one in which electron spins are used for processing and readout while nuclear spins are used for storage. Here we demonstrate the coherent transfer of a superposition state in an electron spin 'processing' qubit to a nuclear spin 'memory' qubit, using a combination of microwave and radiofrequency pulses applied to 31P donors in an isotopically pure 28Si crystal. The electron spin state can be stored in the nuclear spin on a timescale that is long compared with the electron decoherence time and then coherently transferred back to the electron spin, thus demonstrating the 31P nuclear spin as a solid-state quantum memory. The overall store/readout fidelity is about 90%, attributed to systematic imperfections in radiofrequency pulses which can be improved through the use of composite pulses. We apply dynamic decoupling to protect the nuclear spin quantum memory element from sources of decoherence. The coherence lifetime of the quantum memory element is found to exceed one second at 5.5K.Comment: v2: Tomography added and storage of general initial state