Showing papers by "Peidong Yang published in 2014"

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces

Abstract: Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi3 polyhedra, transforms in solution by interior erosion into Pt3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi3 polyhedra are maintained in the final Pt3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skin structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.

Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles

Abstract: Highly efficient and selective electrochemical reduction of carbon dioxide represents one of the biggest scientific challenges in artificial photosynthesis, where carbon dioxide and water are converted into chemical fuels from solar energy. However, our fundamental understanding of the reaction is still limited and we do not have the capability to design an outstanding catalyst with great activity and selectivity a priori. Here we assemble uniform gold-copper bimetallic nanoparticles with different compositions into ordered monolayers, which serve as a well-defined platform to understand their fundamental catalytic activity in carbon dioxide reduction. We find that two important factors related to intermediate binding, the electronic effect and the geometric effect, dictate the activity of gold-copper bimetallic nanoparticles. These nanoparticle monolayers also show great mass activities, outperforming conventional carbon dioxide reduction catalysts. The insights gained through this study may serve as a foundation for designing better carbon dioxide electrochemical reduction catalysts.

25th Anniversary Article: Semiconductor Nanowires – Synthesis, Characterization, and Applications

Abstract: Semiconductor nanowires (NWs) have been studied extensively for over two decades for their novel electronic, photonic, thermal, electrochemical and mechanical properties. This comprehensive review article summarizes major advances in the synthesis, characterization, and application of these materials in the past decade. Developments in the understanding of the fundamental principles of "bottom-up" growth mechanisms are presented, with an emphasis on rational control of the morphology, stoichiometry, and crystal structure of the materials. This is followed by a discussion of the application of nanowires in i) electronic, ii) sensor, iii) photonic, iv) thermoelectric, v) photovoltaic, vi) photoelectrochemical, vii) battery, viii) mechanical, and ix) biological applications. Throughout the discussion, a detailed explanation of the unique properties associated with the one-dimensional nanowire geometry will be presented, and the benefits of these properties for the various applications will be highlighted. The review concludes with a brief perspective on future research directions, and remaining barriers which must be overcome for the successful commercial application of these technologies.

Simultaneously Efficient Light Absorption and Charge Separation in WO3/BiVO4 Core/Shell Nanowire Photoanode for Photoelectrochemical Water Oxidation

Abstract: We report a scalably synthesized WO3/BiVO4 core/shell nanowire photoanode in which BiVO4 is the primary light-absorber and WO3 acts as an electron conductor. These core/shell nanowires achieve the highest product of light absorption and charge separation efficiencies among BiVO4-based photoanodes to date and, even without an added catalyst, produce a photocurrent of 3.1 mA/cm(2) under simulated sunlight and an incident photon-to-current conversion efficiency of ∼ 60% at 300-450 nm, both at a potential of 1.23 V versus RHE.

Evolution of interlayer coupling in twisted molybdenum disulfide bilayers

Abstract: Van der Waals coupling is emerging as a powerful method to engineer physical properties of atomically thin two-dimensional materials. In coupled graphene-graphene and graphene-boron nitride layers, interesting physical phenomena ranging from Fermi velocity renormalization to Hofstadter's butterfly pattern have been demonstrated. Atomically thin transition metal dichalcogenides, another family of two-dimensional-layered semiconductors, can show distinct coupling phenomena. Here we demonstrate the evolution of interlayer coupling with twist angles in as-grown molybdenum disulfide bilayers. We find that the indirect bandgap size varies appreciably with the stacking configuration: it shows the largest redshift for AA- and AB-stacked bilayers, and a significantly smaller but constant redshift for all other twist angles. Our observations, together with ab initio calculations, reveal that this evolution of interlayer coupling originates from the repulsive steric effects that leads to different interlayer separations between the two molybdenum disulfide layers in different stacking configurations.

Semiconductor Nanowires for Artificial Photosynthesis

Abstract: In this Perspective, we discuss current challenges in artificial photosynthesis research, with a focus on the benefits of a nanowire morphology. Matching the flux between electrocatalysts and light-absorbers, and between individual semiconducting light-absorbers, are two major issues to design economically viable devices for artificial photosynthesis. With the knowledge that natural photosynthesis is an integrated nanosystem, individual building blocks of biomimetic artificial photosynthesis are discussed. Possible research directions are presented under an integrated device design scheme, with examples of our current progress in these areas. Coupling all of the components together, including electrocatalysts, light- absorbers, and charge transport units, is crucial due to both fundamental and practical considerations. Given the advantages of one-dimensional nanostructures, it is evident that semiconductor nanowires can function as essential building blocks and help to solve many of the issues in artificial photosynthesis.

Three-Dimensional Spirals of Atomic Layered MoS2

Abstract: Atomically thin two-dimensional (2D) layered materials, including graphene, boron nitride, and transition metal dichalcogenides (TMDs), can exhibit novel phenomena distinct from their bulk counterparts and hold great promise for novel electronic and optoelectronic applications. Controlled growth of such 2D materials with different thickness, composition, and symmetry are of central importance to realize their potential. In particular, the ability to control the symmetry of TMD layers is highly desirable because breaking the inversion symmetry can lead to intriguing valley physics, nonlinear optical properties, and piezoelectric responses. Here we report the first chemical vapor deposition (CVD) growth of spirals of layered MoS2 with atomically thin helical periodicity, which exhibits a chiral structure and breaks the three-dimensional (3D) inversion symmetry explicitly. The spirals composed of tens of connected MoS2 layers with decreasing areas: each basal plane has a triangular shape and shrinks graduall...

Phase-selective cation-exchange chemistry in sulfide nanowire systems.

Abstract: As a cation-deficient, p-type semiconductor, copper sulfide (Cu2–xS) shows promise for applications such as photovoltaics, memristors, and plasmonics. However, these applications demand precise tuning of the crystal phase as well as the stoichiometry of Cu2–xS, an ongoing challenge in the synthesis of Cu2–xS materials for a specific application. Here, a detailed transformation diagram of cation-exchange (CE) chemistry from cadmium sulfide (CdS) into Cu2–xS nanowires (NWs) is reported. By varying the reaction time and the reactants’ concentration ratio, the progression of the CE process was captured, and tunable crystal phases of the Cu2–xS were achieved. It is proposed that the evolution of Cu2–xS phases in a NW system is dependent on both kinetic and thermodynamic factors. The reported data demonstrate that CE can be used to precisely control the structure, composition, and crystal phases of NWs, and such control may be generalized to other material systems for a variety of practical applications.

Semiconductor Nanowires for Artificial Photosynthesis

Abstract: In this Perspective, we discuss current challenges in artificial photosynthesis research, with a focus on the benefits of a nanowire morphology. Matching the flux between electrocatalysts and light-absorbers, and between individual semiconducting light-absorbers, are two major issues to design economically viable devices for artificial photosynthesis. With the knowledge that natural photosynthesis is an integrated nanosystem, individual building blocks of biomimetic artificial photosynthesis are discussed. Possible research directions are presented under an integrated device design scheme, with examples of our current progress in these areas. Coupling all of the components together, including electrocatalysts, light- absorbers, and charge transport units, is crucial due to both fundamental and practical considerations. Given the advantages of one-dimensional nanostructures, it is evident that semiconductor nanowires can function as essential building blocks and help to solve many of the issues in artificial photosynthesis.

All Inorganic Semiconductor Nanowire Mesh for Direct Solar Water Splitting

Abstract: The generation of chemical fuels via direct solar-to-fuel conversion from a fully integrated artificial photosynthetic system is an attractive approach for clean and sustainable energy, but so far there has yet to be a system that would have the acceptable efficiency, durability and can be manufactured at a reasonable cost. Here, we show that a semiconductor mesh made from all inorganic nanowires can achieve unassisted solar-driven, overall water-splitting without using any electron mediators. Free-standing nanowire mesh networks could be made in large scales using solution synthesis and vacuum filtration, making this approach attractive for low cost implementation.

Semiconductor nanowires for photovoltaic and photoelectrochemical energy conversion

Abstract: Semiconductor nanowires (NW) possess several beneficial properties for efficient conversion of solar energy into electricity and chemical energy. Due to their efficient absorption of light, short distances for minority carriers to travel, high surface-to-volume ratios, and the availability of scalable synthesis methods, they provide a pathway to address the low cost-to-power requirements for wide-scale adaptation of solar energy conversion technologies. Here we highlight recent progress in our group towards implementation of NW components as photovoltaic and photoelectrochemical energy conversion devices. An emphasis is placed on the unique properties of these one-dimensional (1D) structures, which enable the use of abundant, low-cost materials and improved energy conversion efficiency compared to bulk devices.

Epitaxially Aligned Cuprous Oxide Nanowires for All-Oxide, Single-Wire Solar Cells

Abstract: As a p-type semiconducting oxide that can absorb visible light, cuprous oxide (Cu2O) is an attractive material for solar energy conversion. This work introduces a high-temperature, vapor-phase synthesis that produces faceted Cu2O nanowires that grow epitaxially along the surface of a lattice-matched, single-crystal MgO substrate. Individual wires were then fabricated into single-wire, all-oxide diodes and solar cells using low-temperature atomic layer deposition (ALD) of TiO2 and ZnO films to form the heterojunction. The performance of devices made from pristine Cu2O wires and chlorine-exposed Cu2O wires was investigated under one-sun and laser illumination. These faceted wires allow the fabrication of well-controlled heterojunctions that can be used to investigate the interfacial properties of all-oxide solar cells.

Uniform Doping of Metal Oxide Nanowires Using Solid State Diffusion

Abstract: The synthesis of one-dimensional nanostructures with specific properties is often hindered by difficulty in tuning the material composition without sacrificing morphology and material quality. Here, we present a simple solid state diffusion method utilizing atomic layer deposition to controllably alter the composition of metal oxide nanowires. This compositional control allows for modification of the optical, electronic, and electrochemical properties of the semiconductor nanowires. Using this method and a novel process for manganese oxide atomic layer deposition, we produced manganese-doped rutile TiO2 nanowires and investigated their structural and photoelectrochemical properties. A homogeneous incorporation of the Mn dopant into the rutile lattice was observed, and the local chemical environment of the Mn was determined using X-ray absorption spectroscopy. The doping process resulted in a tunable enhancement in the electrocatalytic activity for water oxidation, demonstrating that this simple and general method can be used to control the properties of one-dimensional nanostructures for use in a variety of applications including solar-to-fuel generation.

Salt-Induced Self-Assembly of Bacteria on Nanowire Arrays

Abstract: Studying bacteria-nanostructure interactions is crucial to gaining controllable interfacing of biotic and abiotic components in advanced biotechnologies. For bioelectrochemical systems, tunable cell-electrode architectures offer a path toward improving performance and discovering emergent properties. As such, Sporomusa ovata cells cultured on vertical silicon nanowire arrays formed filamentous cells and aligned parallel to the nanowires when grown in increasing ionic concentrations. Here, we propose a model describing the kinetic and the thermodynamic driving forces of bacteria-nanowire interactions.

25th Anniversary Article: Semiconductor Nanowires — Synthesis, Characterization, and Applications

Abstract: Semiconductor nanowires (NWs) have been studied extensively for over two decades for their novel electronic, photonic, thermal, electrochemical and mechanical properties. This comprehensive review article summarizes major advances in the synthesis, characterization, and application of these materials in the past decade. Developments in the understanding of the fundamental principles of "bottom-up" growth mechanisms are presented, with an emphasis on rational control of the morphology, stoichiometry, and crystal structure of the materials. This is followed by a discussion of the application of nanowires in i) electronic, ii) sensor, iii) photonic, iv) thermoelectric, v) photovoltaic, vi) photoelectrochemical, vii) battery, viii) mechanical, and ix) biological applications. Throughout the discussion, a detailed explanation of the unique properties associated with the one-dimensional nanowire geometry will be presented, and the benefits of these properties for the various applications will be highlighted. The review concludes with a brief perspective on future research directions, and remaining barriers which must be overcome for the successful commercial application of these technologies.

Alumina-coated Ag nanocrystal monolayers as surfaceenhanced Raman spectroscopy platforms for the direct spectroscopic detection of water splitting reaction intermediates

Abstract: A novel Ag-alumina hybrid surface-enhanced Raman spectroscopy (SERS) platform has been designed for the spectroscopic detection of surface reactions in the steady state. Single crystalline and faceted silver (Ag) nanoparticles with strong light scattering were prepared in large quantity, which enables their reproducible self-assembly into large scale monolayers of Raman sensor arrays by the Langmuir-Blodgett technique. The close packed sensor film contains high density of sub-nm gaps between sharp edges of Ag nanoparticles, which created large local electromagnetic fields that serve as “hot spots” for SERS enhancement. The SERS substrate was then coated with a thin layer of alumina by atomic layer deposition to prevent charge transfer between Ag and the reaction system. The photocatalytic water splitting reaction on a monolayer of anatase TiO2 nanoplates decorated with Pt co-catalyst nanoparticles was employed as a model reaction system. Reaction intermediates of water photo-oxidation were observed at the TiO2/solution interface under UV irradiation. The surface-enhanced Raman vibrations corresponding to peroxo, hydroperoxo and hydroxo surface intermediate species were observed on the TiO2 surface, suggesting that the photo-oxidation of water on these anatase TiO2 nanosheets may be initiated by a nucleophilic attack mechanism.

Chapter 6:Nanowires for Photovoltaics and Artificial Photosynthesis

Abstract: As the world's population grows and modernizes, developing inexpensive and efficient technologies for solar energy conversion is becoming increasingly important. Photovoltaics and artificial photosynthesis are two approaches for transforming solar energy into a usable form, either electricity or chemical fuels. While both technologies have been actively researched for decades, semiconductor nanowires possess unique properties that make them promising candidates for efficient photovoltaics and artificial photosynthesis. Because many optical and electronic processes occur over nanometer length scales, nanowires can offer improved capabilities to absorb light, collect photogenerated charges, and perform chemical reactions, functions that are all essential for solar energy conversion. Additionally, the increasing dexterity with which scientists synthesize, fabricate, and integrate nanoscale structures suggests that efficient devices that can take full advantage of these unique properties are not too far in the future.

Thermoelectric device comprising nanostructures and method of operating said device

Abstract: PROBLEM TO BE SOLVED: To provide a nanostructure having a rough surface and comprising a doped or undoped semiconductor.SOLUTION: The invention provides a nanostructure, and an array of a plurality of nanostructures, each having a rough surface and comprising a doped or undoped semiconductor. The nanostructure is a one-dimensional (1-D) nanostructure, such a nanowire, or a two-dimensional (2-D) nanostructure. The nanostructure can be placed between two electrodes and used for thermoelectric power generation or thermoelectric cooling.

Introductory lecture: Systems materials engineering approach for solar-to-chemical conversion

Abstract: Solar-to-chemical (STC) production using a fully integrated system is an attractive goal, but to-date there has yet to be a system that can demonstrate the required efficiency or durability, or could be manufactured at a reasonable cost. One can learn a great deal from the natural photosynthesis where the conversion of carbon dioxide and water to carbohydrates is routinely carried out at a highly coordinated system level. There are several key features worth mentioning in these systems: spatial and directional arrangement of the light-harvesting components; charge separation and transport; as well as the desired chemical conversion at catalytic sites in compartmentalized spaces. In order to design an efficient artificial photosynthetic materials system, at the level of the individual components better catalysts need to be developed, new light-absorbing semiconductor materials will need to be discovered, architectures will need to be designed for effective capture and conversion of sunlight, and more importantly, processes need to be developed for the efficient coupling and integration of the components into a complete artificial photosynthetic system.