Nathan S. Lewis

Bio: Nathan S. Lewis is an academic researcher from California Institute of Technology. The author has contributed to research in topics: Semiconductor & Silicon. The author has an hindex of 112, co-authored 720 publications receiving 64808 citations. Previous affiliations of Nathan S. Lewis include Lawrence Berkeley National Laboratory & Massachusetts Institute of Technology.

Anchoring Group and Auxiliary Ligand Effects on the Binding of Ruthenium Complexes to Nanocrystalline TiO2 Photoelectrodes

Abstract: The thermodynamics and kinetics of binding to nanocrystalline TiO_2 were investigated for five ruthenium complexes that differed structurally in the number of possible anchoring carboxy groups (one, two, four, or six) attached to coordinated bipyridyl ligands and in the number of auxiliary ligands (bipyridine, CN-, or SCN-). Diffuse reflectance infrared spectroscopic data indicated that the dyes predominantly bound to TiO_2 in a bridging mode in which the oxygen atoms of an attached carboxy group were bound to separate titanium atoms on the TiO_2 surface. Furthermore, in the dry state, complexes with only one monocarboxy or dicarboxy ligand used essentially all of their available carboxy groups to bind to the surface. However, complexes having two or three dicarboxy ligands used on average two carboxylato groups in binding to TiO_2. The structural differences between the complexes were manifested chemically in that the five dyes yielded similar maximum coverages (>100 nmol cm^(-2)) on nanocrystalline TiO_2 electrodes, but exhibited different binding constants (10^3−10^5 M^(-1)) and different adsorption and desorption kinetics (3−11) × 10^3 M^(-1) h^(-1) and 1−100 h, respectively). The binding constant for the monocarboxy dye was significantly lower than the binding constants for dyes with dicarboxy ligands, correlating primarily with an increase in the desorption rate of the monocarboxy complex. The adsorption rate constants were similar for all of the dyes, suggesting that formation of the first bond to TiO_2 was rate limiting. Binding of the dyes from an ethanolic solution that contained pyridine and pyridinium as an acidic proton activity buffer yielded lower coverages than binding from a nonbuffered ethanol solution, even though the binding constants were up to 100 times greater under buffered conditions. The lower equilibrium dye coverage in buffered ethanol did not correlate with changes in the protonation state of the dyes but rather indicated competition for, and/or deactivation of, TiO_2 active sites in buffered ethanol. The more weakly bound monocarboxy dye displayed the lowest short-circuit current density and open-circuit voltage under simulated solar illumination in a photoelectrochemical cell containing 0.50 M LiI, 0.040 M I_2, 0.020 M pyridine, and 0.020 M pyridinium triflate in acetonitrile. Additionally, even at constant coverage, the integrated quantum yield for photocurrent flow was lowest for TiO_2 sensitized with the monocarboxy dye. The potential required to drive 0.1 mA cm^(-2) of cathodic current density in the dark on dye-sensitized TiO_2 photoelectrodes was least negative for the monocarboxy dye, indicating more facile electron transfer between reduced TiO_2 and the solution redox couple. Hence, in this series of ruthenium carboxy-bipyridyl dyes, the most weakly bound species (i.e., the monocarboxy dye) yielded inferior photoelectrode properties, whereas differences between the dyes that contained at least one dicarboxy ligand resulted primarily from differences in the light absorption and energetic properties of the metal complexes. These observations suggest an important role for the linkage to the TiO_2 surface in achieving temporal stability as well as in tuning both the steady-state quantum yield and the magnitude of the predominant back-reaction rate in dye-sensitized TiO_2-based photoelectrochemical solar cells.

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Abstract: Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogen-evolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η, of -η < 100 mV at a current density of -10 mA cm-2 in 0.500 M H2SO4(aq). To obtain a chemical description of the material as-prepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H2SO4(aq). Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.

Chemical and Electrical Passivation of Silicon (111) Surfaces through Functionalization with Sterically Hindered Alkyl Groups

Abstract: Crystalline Si(111) surfaces have been alkylated in a two-step chlorination/alkylation process using sterically bulky alkyl groups such as (CH3)2CH− (iso-propyl), (CH3)3C− (tert-butyl), and C6H5− (phenyl) moieties. X-ray photoelectron spectroscopic (XPS) data in the C 1s region of such surfaces exhibited a low energy emission at 283.9 binding eV, consistent with carbon bonded to Si. The C 1s XPS data indicated that the alkyls were present at lower coverages than methyl groups on CH3-terminated Si(111) surfaces. Despite the lower alkyl group coverage, no Cl was detected after alkylation. Functionalization with the bulky alkyl groups effectively inhibited the oxidation of Si(111) surfaces in air and produced low (<100 cm s-1) surface recombination velocities. Transmission infrared spectroscopy indicated that the surfaces were partially H-terminated after the functionalization reaction. Application of a reducing potential, −2.5 V vs Ag+/Ag, to Cl-terminated Si(111) electrodes in tetrahydrofuran resulted in t...

Electrochemical properties of (111)-oriented n-si surfaces derivatized with covalently-attached alkyl chains

Abstract: The electrochemical properties of alkyl-terminated, (111)-oriented, n-type Si surfaces, prepared via a two-step halogenation/alkylation procedure, were analyzed in contact with CH3OH−1,1‘-dimethylferrocene+/0 (Me2Fc+/0) solutions. Current density−potential and differential capacitance−potential measurements of these surfaces in contact with CH3OH−Me2Fc+/0 indicated that the electrochemical properties of the alkyl-terminated surfaces were very similar to those of the H-terminated Si surface. The alkyl overlayers did not shift the Si band edges or induce significant surface recombination, but they did provide an additional electrical series resistance to charge transfer across the Si/liquid interface. The efficacy of alkyl overlayers in preventing photooxidation and photocorrosion of n-silicon surfaces was measured in contact with CH3OH−Me2Fc+/0 solutions to which a known amount of water had been added. Under these conditions, the alkyl-terminated surfaces consistently showed excellent current density−poten...

Modeling, Simulation, and Implementation of Solar-Driven Water-Splitting Devices.

Abstract: An integrated cell for the solar-driven splitting of water consists of multiple functional components and couples various photoelectrochemical (PEC) processes at different length and time scales. The overall solar-to-hydrogen (STH) conversion efficiency of such a system depends on the performance and materials properties of the individual components as well as on the component integration, overall device architecture, and system operating conditions. This Review focuses on the modeling- and simulation-guided development and implementation of solar-driven water-splitting prototypes from a holistic viewpoint that explores the various interplays between the components. The underlying physics and interactions at the cell level is are reviewed and discussed, followed by an overview of the use of the cell model to provide target properties of materials and guide the design of a range of traditional and unique device architectures.

I and i

Abstract: There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality. Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films

Abstract: THE large-scale use of photovoltaic devices for electricity generation is prohibitively expensive at present: generation from existing commercial devices costs about ten times more than conventional methods1. Here we describe a photovoltaic cell, created from low-to medium-purity materials through low-cost processes, which exhibits a commercially realistic energy-conversion efficiency. The device is based on a 10-µm-thick, optically transparent film of titanium dioxide particles a few nanometres in size, coated with a monolayer of a charge-transfer dye to sensitize the film for light harvesting. Because of the high surface area of the semiconductor film and the ideal spectral characteristics of the dye, the device harvests a high proportion of the incident solar energy flux (46%) and shows exceptionally high efficiencies for the conversion of incident photons to electrical current (more than 80%). The overall light-to-electric energy conversion yield is 7.1-7.9% in simulated solar light and 12% in diffuse daylight. The large current densities (greater than 12 mA cm-2) and exceptional stability (sustaining at least five million turnovers without decomposition), as well as the low cost, make practical applications feasible.

疟原虫var基因转换速率变化导致抗原变异[英]／Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A

Abstract: 抗原变异可使得多种致病微生物易于逃避宿主免疫应答。表达在感染红细胞表面的恶性疟原虫红细胞表面蛋白1（PfPMP1）与感染红细胞、内皮细胞、树突状细胞以及胎盘的单个或多个受体作用，在黏附及免疫逃避中起关键的作用。每个单倍体基因组var基因家族编码约60种成员，通过启动转录不同的var基因变异体为抗原变异提供了分子基础。

Heterogeneous photocatalyst materials for water splitting

Abstract: This critical review shows the basis of photocatalytic water splitting and experimental points, and surveys heterogeneous photocatalyst materials for water splitting into H2 and O2, and H2 or O2 evolution from an aqueous solution containing a sacrificial reagent Many oxides consisting of metal cations with d0 and d10 configurations, metal (oxy)sulfide and metal (oxy)nitride photocatalysts have been reported, especially during the latest decade The fruitful photocatalyst library gives important information on factors affecting photocatalytic performances and design of new materials Photocatalytic water splitting and H2 evolution using abundant compounds as electron donors are expected to contribute to construction of a clean and simple system for solar hydrogen production, and a solution of global energy and environmental issues in the future (361 references)