Showing papers in "Accounts of Chemical Research in 2013"

Single-atom catalysts: a new frontier in heterogeneous catalysis.

Abstract: Supported metal nanostructures are the most widely used type of heterogeneous catalyst in industrial processes. The size of metal particles is a key factor in determining the performance of such catalysts. In particular, because low-coordinated metal atoms often function as the catalytically active sites, the specific activity per metal atom usually increases with decreasing size of the metal particles. However, the surface free energy of metals increases significantly with decreasing particle size, promoting aggregation of small clusters. Using an appropriate support material that strongly interacts with the metal species prevents this aggregation, creating stable, finely dispersed metal clusters with a high catalytic activity, an approach industry has used for a long time. Nevertheless, practical supported metal catalysts are inhomogeneous and usually consist of a mixture of sizes from nanoparticles to subnanometer clusters. Such heterogeneity not only reduces the metal atom efficiency but also frequent...

Roles of cocatalysts in photocatalysis and photoelectrocatalysis.

Abstract: Since the 1970s, splitting water using solar energy has been a focus of great attention as a possible means for converting solar energy to chemical energy in the form of clean and renewable hydrogen fuel. Approaches to solar water splitting include photocatalytic water splitting with homogeneous or heterogeneous photocatalysts, photoelectrochemical or photoelectrocatalytic (PEC) water splitting with a PEC cell, and electrolysis of water with photovoltaic cells coupled to electrocatalysts. Though many materials are capable of photocatalytically producing hydrogen and/or oxygen, the overall energy conversion efficiency is still low and far from practical application. This is mainly due to the fact that the three crucial steps for the water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic reduction and oxidation reactions, are not efficient enough or simultaneously. Water splitting is a thermodynamically uphill reaction, requiring transfer of multiple electrons, making it one of the most challenging reactions in chemistry. This Account describes the important roles of cocatalysts in photocatalytic and PEC water splitting reactions. For semiconductor-based photocatalytic and PEC systems, we show that loading proper cocatalysts, especially dual cocatalysts for reduction and oxidation, on semiconductors (as light harvesters) can significantly enhance the activities of photocatalytic and PEC water splitting reactions. Loading oxidation and/or reduction cocatalysts on semiconductors can facilitate oxidation and reduction reactions by providing the active sites/reaction sites while suppressing the charge recombination and reverse reactions. In a PEC water splitting system, the water oxidation and reduction reactions occur at opposite electrodes, so cocatalysts loaded on the electrode materials mainly act as active sites/reaction sites spatially separated as natural photosynthesis does. In both cases, the nature of the loaded cocatalysts and their interaction with the semiconductor through the interface/junction are important. The cocatalyst can provide trapping sites for the photogenerated charges and promote the charge separation, thus enhancing the quantum efficiency; the cocatalysts could improve the photostability of the catalysts by timely consuming of the photogenerated charges, particularly the holes; most importantly, the cocatalysts catalyze the reactions by lowering the activation energy. Our research shows that loading suitable dual cocatalysts on semiconductors can significantly increase the photocatalytic activities of hydrogen and oxygen evolution reactions, and even make the overall water splitting reaction possible. All of these findings suggest that dual cocatalysts are necessary for developing highly efficient photocatalysts for water splitting reactions.

Challenges and prospects of lithium-sulfur batteries.

Abstract: Electrical energy storage is one of the most critical needs of 21st century society. Applications that depend on electrical energy storage include portable electronics, electric vehicles, and devices for renewable energy storage from solar and wind. Lithium-ion (Li-ion) batteries have the highest energy density among the rechargeable battery chemistries. As a result, Li-ion batteries have proven successful in the portable electronics market and will play a significant role in large-scale energy storage. Over the past two decades, Li-ion batteries based on insertion cathodes have reached a cathode capacity of ∼250 mA h g(-1) and an energy density of ∼800 W h kg(-1), which do not meet the requirement of ∼500 km between charges for all-electric vehicles. With a goal of increasing energy density, researchers are pursuing alternative cathode materials such as sulfur and O2 that can offer capacities that exceed those of conventional insertion cathodes, such as LiCoO2 and LiMn2O4, by an order of magnitude (>1500 mA h g(-1)). Sulfur, one of the most abundant elements on earth, is an electrochemically active material that can accept up to two electrons per atom at ∼2.1 V vs Li/Li(+). As a result, sulfur cathode materials have a high theoretical capacity of 1675 mA h g(-1), and lithium-sulfur (Li-S) batteries have a theoretical energy density of ∼2600 W h kg(-1). Unlike conventional insertion cathode materials, sulfur undergoes a series of compositional and structural changes during cycling, which involve soluble polysulfides and insoluble sulfides. As a result, researchers have struggled with the maintenance of a stable electrode structure, full utilization of the active material, and sufficient cycle life with good system efficiency. Although researchers have made significant progress on rechargeable Li-S batteries in the last decade, these cycle life and efficiency problems prevent their use in commercial cells. To overcome these persistent problems, researchers will need new sulfur composite cathodes with favorable properties and performance and new Li-S cell configurations. In this Account, we first focus on the development of novel composite cathode materials including sulfur-carbon and sulfur-polymer composites, describing the design principles, structure and properties, and electrochemical performances of these new materials. We then cover new cell configurations with carbon interlayers and Li/dissolved polysulfide cells, emphasizing the potential of these approaches to advance capacity retention and system efficiency. Finally, we provide a brief survey of efficient electrolytes. The Account summarizes improvements that could bring Li-S technology closer to mass commercialization.

Bioprobes Based on AIE Fluorogens

Abstract: Fluorescent bioprobes are powerful tools for analytical sensing and optical imaging, which allow direct visualization of biological analytes at the molecular level and offer useful insights into complex biological structures and processes. The sensing and imaging sensitivity of a bioprobe is determined by the brightness and contrast of its fluorescence before and after analyte binding. Emission from a fluorophore is often quenched at high concentration or in aggregate state, which is notoriously known as concentration quenching or aggregation-caused quenching (ACQ). The ACQ effect limits the label-to-analyte ratio and forces researchers to use very dilute solutions of fluorophores. It compels many probes to operate in a fluorescence “turn-off” mode with a narrow scope of practical applications.The unique aggregation-induced emission (AIE) process offers a straightforward solution to the ACQ problem. Typical AIE fluorogens are characterized by their propeller-shaped rotorlike structures, which undergo low-...

Biomedical Applications of Graphene and Graphene Oxide

Abstract: Graphene has unique mechanical, electronic, and optical properties, which researchers have used to develop novel electronic materials including transparent conductors and ultrafast transistors. Recently, the understanding of various chemical properties of graphene has facilitated its application in high-performance devices that generate and store energy. Graphene is now expanding its territory beyond electronic and chemical applications toward biomedical areas such as precise biosensing through graphene-quenched fluorescence, graphene-enhanced cell differentiation and growth, and graphene-assisted laser desorption/ionization for mass spectrometry. In this Account, we review recent efforts to apply graphene and graphene oxides (GO) to biomedical research and a few different approaches to prepare graphene materials designed for biomedical applications. Because of its excellent aqueous processability, amphiphilicity, surface functionalizability, surface enhanced Raman scattering (SERS), and fluorescence quenching ability, GO chemically exfoliated from oxidized graphite is considered a promising material for biological applications. In addition, the hydrophobicity and flexibility of large-area graphene synthesized by chemical vapor deposition (CVD) allow this material to play an important role in cell growth and differentiation. The lack of acceptable classification standards of graphene derivatives based on chemical and physical properties has hindered the biological application of graphene derivatives. The development of an efficient graphene-based biosensor requires stable biofunctionalization of graphene derivatives under physiological conditions with minimal loss of their unique properties. For the development graphene-based therapeutics, researchers will need to build on the standardization of graphene derivatives and study the biofunctionalization of graphene to clearly understand how cells respond to exposure to graphene derivatives. Although several challenging issues remain, initial promising results in these areas point toward significant potential for graphene derivatives in biomedical research.

Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems

Abstract: Securing our energy future is the most important problem that humanity faces in this century. Burning fossil fuels is not sustainable, and wide use of renewable energy sources will require a drastically increased ability to store electrical energy. In the move toward an electrical economy, chemical (batteries) and capacitive energy storage (electrochemical capacitors or supercapacitors) devices are expected to play an important role. This Account summarizes research in the field of electrochemical capacitors conducted over the past decade.Overall, the combination of the right electrode materials with a proper electrolyte can successfully increase both the energy stored by the device and its power, but no perfect active material exists and no electrolyte suits every material and every performance goal. However, today, many materials are available, including porous activated, carbide-derived, and templated carbons with high surface areas and porosities that range from subnanometer to just a few nanometers. ...

Review of chemical vapor deposition of graphene and related applications.

Abstract: Since its debut in 2004, graphene has attracted enormous interest because of its unique properties. Chemical vapor deposition (CVD) has emerged as an important method for the preparation and production of graphene for various applications since the method was first reported in 2008/2009. In this Account, we review graphene CVD on various metal substrates with an emphasis on Ni and Cu. In addition, we discuss important and representative applications of graphene formed by CVD, including as flexible transparent conductors for organic photovoltaic cells and in field effect transistors.Growth on polycrystalline Ni films leads to both monolayer and few-layer graphene with multiple layers because of the grain boundaries on Ni films. We can greatly increase the percentage of monolayer graphene by using single-crystalline Ni(111) substrates, which have smooth surface and no grain boundaries. Due to the extremely low solubility of carbon in Cu, Cu has emerged as an even better catalyst for the growth of monolayer ...

New approaches for high energy density lithium-sulfur battery cathodes.

Abstract: The goal of replacing combustion engines or reducing their use presents a daunting problem for society. Current lithium-ion technologies provide a stepping stone for this dramatic but inevitable change. However, the theoretical gravimetric capacity (∼300 mA h g–1) is too low to overcome the problems of limited range in electric vehicles, and their cost is too high to sustain the commercial viability of electrified transportation. Sulfur is the one of the most promising next generation cathode materials. Since the 1960s, researchers have studied sulfur as a cathode, but only recently have great strides been made in preparing viable composites that can be used commercially. Sulfur batteries implement inexpensive, earth-abundant elements at the cathode while offering up to a five-fold increase in energy density compared with present Li-ion batteries.Over the past few years, researchers have come closer to solving the challenges associated with the sulfur cathode. Using carbon or conducting polymers, research...

Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction

Abstract: Platinum-based catalysts represent a state of the art in the electrocatalysis of oxygen reduction reaction (ORR) from the point of view of their activity and durability in harnessing the chemical energy via direct electrochemical conversion. However, because platinum is both expensive and scarce, its widespread implementation in such clean energy applications is limited. Recent breakthroughs in the synthesis of high-performance nonprecious metal catalysts (NPMCs) make replacement of Pt in ORR electrocatalysts with earth-abundant elements, such as Fe, Co, N, and C, a realistic possibility. In this Account, we discuss how we can obtain highly promising M–N–C (M: Fe and/or Co) catalysts by simultaneously heat-treating precursors of nitrogen, carbon, and transition metals at 800–1000 °C. The activity and durability of resulting catalysts depend greatly on the selection of precursors and synthesis chemistry. In addition, they correlate quite well with the catalyst nanostructure. While chemists have presented n...

Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?

Abstract: Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental understanding of catalyst sintering is very important for achieving clean energy and a clean environment, and for efficient chemical conversion processes with atom selectivity. Scientists have proposed two mechanisms for sintering of nanoparticles: particle migration and coalescence (PMC) and Ostwald ripening (OR). PMC involves the mobility of particles in a Brownian-like motion on the support surface, with subsequent coalescence leading to nanoparticle growth. In contrast, OR involves the migration of adatoms or mobile molecular species, driven by differences in free energy and local adatom concentrations on the support surface. In this Account, we divide the process of sintering into three phases. Phase I involves rapid loss in catalyst activity (or surface area), phase II is where sintering slows down, and phase III is where the catalyst may reach a stable performance. Much of the previous work is based on inferences from catalysts that were observed before and after long term treatments. While the general phenomena can be captured correctly, the mechanisms cannot be determined. Advancements in the techniques of in situ TEM allow us to observe catalysts at elevated temperatures under working conditions. We review recent evidence obtained via in situ methods to determine the relative importance of PMC and OR in each of these phases of catalyst sintering. The evidence suggests that, in phase I, OR is responsible for the rapid loss of activity that occurs when particles are very small. Surprisingly, very little PMC is observed in this phase. Instead, the rapid loss of activity is caused by the disappearance of the smallest particles. These findings are in good agreement with representative atomistic simulations of sintering. In phase II, sintering slows down since the smallest particles have disappeared. We now see a combination of PMC and OR, but do not fully understand the relative contribution of each of these processes to the overall rates of sintering. In phase III, the particles have grown large and other parasitic phenomena, such as support restructuring, can become important, especially at high temperatures. Examining the evolution of particle size and surface area with time, we do not see a stable or equilibrium state, especially for catalysts operating at elevated temperatures. In conclusion, the recent literature, especially on in situ studies, shows that OR is the dominant process causing the growth of nanoparticle size. Consequently, this leads to the loss of surface area and activity. While particle migration could be controlled through suitable structuring of catalyst supports, it is more difficult to control the mobility of atomically dispersed species. These insights into the mechanisms of sintering could help to develop sinter-resistant catalysts, with the ultimate goal of designing catalysts that are self-healing.

The Cation-π Interaction

Abstract: The chemistry community now recognizes the cation−π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug–receptor interactions. This Account provides the author’s perspective on the intellectual origins and fundamental nature of the cation−π interaction.Early studies on cyclophanes established that water-soluble, cationic molecules would forego aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation−π interaction. The strength of the cation−π interaction (Li+ binds to benzene with 38 kcal/mol of binding energy; NH4+ with 19 kcal/mol) distinguishes it from the weaker polar−π interactions observed in the benzene dimer or water–benzene complexes. In addition to the substantial intrinsic strength of the cation−π interaction in gas phase studies, the cation−π interaction remains energ...

Liquid Exfoliation of Defect-Free Graphene

Abstract: Due to its unprecedented physical properties, graphene has generated huge interest over the last 7 years. Graphene is generally fabricated in one of two ways: as very high quality sheets produced in limited quantities by micromechanical cleavage or vapor growth or as a rather defective, graphene-like material, graphene oxide, produced in large quantities. However, a growing number of applications would profit from the availability of a method to produce high-quality graphene in large quantities.This Account describes recent work to develop such a processing route inspired by previous theoretical and experimental studies on the solvent dispersion of carbon nanotubes. That work had shown that nanotubes could be effectively dispersed in solvents whose surface energy matched that of the nanotubes. We describe the application of the same approach to the exfoliation of graphite to give graphene in a range of solvents. When graphite powder is exposed to ultrasonication in the presence of a suitable solvent, the ...

Platinum-based oxygen reduction electrocatalysts.

Abstract: An efficient oxygen reduction reaction (ORR) offers the potential for clean energy generation in low-temperature, proton-exchange membrane fuel cells running on hydrogen fuel and air. In the past several years, researchers have developed high-performance electrocatalysts for the ORR to address the obstacles of high cost of the Pt catalyst per kilowatt of output power and of declining catalyst activity over time. Current efforts are focused on new catalyst structures that add a secondary metal to change the d-band center and the surface atomic arrangement of the catalyst, altering the chemisorption of those oxygencontaining species that have the largest impact on the ORR kinetics and improving the catalyst activity and cost effectiveness.This Account reviews recent progress in the design of Pt-based ORR electrocatalysts, including improved understanding of the reaction mechanisms and the development of synthetic methods for producing catalysts with high activity and stability. Researchers have made several...

Atomically Precise Gold Nanoclusters as New Model Catalysts

Abstract: Many industrial catalysts involve nanoscale metal particles (typically 1–100 nm), and understanding their behavior at the molecular level is a major goal in heterogeneous catalyst research. However, conventional nanocatalysts have a nonuniform particle size distribution, while catalytic activity of nanoparticles is size dependent. This makes it difficult to relate the observed catalytic performance, which represents the average of all particle sizes, to the structure and intrinsic properties of individual catalyst particles. To overcome this obstacle, catalysts with well-defined particle size are highly desirable.In recent years, researchers have made remarkable advances in solution-phase synthesis of atomically precise nanoclusters, notably thiolate-protected gold nanoclusters. Such nanoclusters are composed of a precise number of metal atoms (n) and of ligands (m), denoted as Aun(SR)m, with n ranging up to a few hundred atoms (equivalent size up to 2–3 nm). These protected nanoclusters are well-defined ...

Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

Abstract: Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon–carbon bond-forming methodologies.Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon–carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role i...

FRET-based small-molecule fluorescent probes: rational design and bioimaging applications.

Abstract: Fluorescence imaging has emerged as a powerful tool for monitoring biomolecules within the context of living systems with high spatial and temporal resolution. Researchers have constructed a large number of synthetic intensity-based fluorescent probes for bio-imaging. However, intensity-based fluorescent probes have some limitations: variations in probe concentration, probe environment, and excitation intensity may influence the fluorescence intensity measurements. In principle, the use of ratiometric fluorescent probes can alleviate this shortcoming. Forster resonance energy transfer (FRET) is one of the most widely used sensing mechanisms for ratiometric fluorescent probes. However, the development of synthetic FRET probes with favorable photophysical properties that are also suitable for biological imaging applications remains challenging. In this Account, we review the rational design and biological applications of synthetic FRET probes, focusing primarily on studies from our laboratory. To construct useful FRET probes, it is a pre-requisite to develop a FRET platform with favorable photophysical properties. The design criteria of a FRET platform include (1) well-resolved absorption spectra of the donor and acceptor, (2) well-separated emission spectra of the donor and acceptor, (3) donors and acceptors with comparable brightness, (4) rigid linkers, and (5) near-perfect efficiency in energy transfer. With an efficient FRET platform in hand, it is then necessary to modulate the donor-acceptor distance or spectral overlap integral in an analyte-dependent fashion for development of FRET probes. Herein, we emphasize our most recent progress on the development of FRET probes by spectral overlap integral, in particular by changing the molar absorption coefficient of the donor dyes such as rhodamine dyes, which undergo unique changes in the absorption profiles during the ring-opening and -closing processes. Although partial success has been obtained in design of first-generation rhodamine-based FRET probes via modulation of acceptor molar absorption coefficient, further improvements in terms of versatility, sensitivity, and synthetic accessibility are required. To address these issues with the first-generation rhodamine-based FRET probes, we have proposed a strategy for the design of second-generation probes. As a demonstration, we have developed FRET imaging probes for diverse targets including Cu²⁺, NO, HOCl, cysteine, and H₂O₂. This discussion of the methods for successfully designing synthetic FRET probes underscores the rational basis for further development of new FRET probes as a molecular toolbox for probing and manipulating a wide variety of biomolecules in living systems.

Mesoporous Silica Nanoparticle Nanocarriers: Biofunctionality and Biocompatibility

Abstract: The study of ordered mesoporous silica materials has exploded since their discovery by Mobil researchers 20 years ago. The ability to make uniformly sized, porous, and dispersible nanoparticles using colloidal chemistry and evaporation-induced self-assembly has led to many applications of mesoporous silica nanoparticles (MSNPs) as "nanocarriers" for delivery of drugs and other cargos to cells. The exceptionally high surface area of MSNPs, often exceeding 1000 m²/g, and the ability to independently modify pore size and surface chemistry, enables the loading of diverse cargos and cargo combinations at levels exceeding those of other common drug delivery carriers such as liposomes or polymer conjugates. This is because noncovalent electrostatic, hydrogen-bonding, and van der Waals interactions of the cargo with the MSNP internal surface cause preferential adsorption of cargo to the MSNP, allowing loading capacities to surpass the solubility limit of a solution or that achievable by osmotic gradient loading. The ability to independently modify the MSNP surface and interior makes possible engineered biofunctionality and biocompatibility. In this Account, we detail our recent efforts to develop MSNPs as biocompatible nanocarriers (Figure 1 ) that simultaneously display multiple functions including (1) high visibility/contrast in multiple imaging modalities, (2) dispersibility, (3) binding specificity to a particular target tissue or cell type, (4) ability to load and deliver large concentrations of diverse cargos, and (5) triggered or controlled release of cargo. Toward function 1, we chemically conjugated fluorescent dyes or incorporated magnetic nanoparticles to enable in vivo optical or magnetic resonance imaging. For function 2, we have made MSNPs with polymer coatings, charged groups, or supported lipid bilayers, which decrease aggregation and improve stability in saline solutions. For functions 3 and 4, we have enhanced passive bioaccumulation via the enhanced permeability and retention effect by modifying the MSNP surfaces with positively charged polymers. We have also chemically attached ligands to MSNPs that selectively bind to receptors overexpressed in cancer cells. We have used encapsulation of MSNPs within reconfigurable supported lipid bilayers to develop new classes of responsive nanocarriers that actively interact with the target cell. Toward function 4, we exploit the high surface area and tailorable surface chemistry of MSNPs to retain hydrophobic drugs. Finally, for function 5, we have engineered dynamic behaviors by incorporating molecular machines within or at the entrances of MSNP pores and by using ligands, polymers, or lipid bilayers. These provide a means to seal-in and retain cargo and to direct MSNP interactions with and internalization by target cells. Application of MSNPs as nanocarriers requires biocompatibility and low toxicity. Here the intrinsic porosity of the MSNP surface reduces the extent of hydrogen bonding or electrostatic interactions with cell membranes as does surface coating with polymers or lipid bilayers. Furthermore, the high surface area and low extent of condensation of the MSNP siloxane framework promote a high rate of dissolution into soluble silicic acid species, which are found to be nontoxic. Potential toxicity is further mitigated by the high drug capacity of MSNPs, which greatly reduces needed dosages compared with other nanocarriers. We anticipate that future generations of MSNPs incorporating molecular machines and encapsulated by membrane-like lipid bilayers will achieve a new level of controlled cellular interactions.

Functionalization of Graphene for Efficient Energy Conversion and Storage

Abstract: As global energy consumption accelerates at an alarming rate, the develop- ment of clean and renewable energy conversion and storage systems has become more important than ever. Although the efficiency of energy conversion and storage devices depends on a variety of factors, their overall performance strongly relies on the structure and properties of the component materials. Nanotechnology has opened up new frontiers in materials science and engineering to meet this challenge by creating new materials, particularly carbon nanomaterials, for efficient energy conversion and storage.As a building block for carbon materials of all other dimensionalities (such as 0D buckyball, 1D nanotube, 3D graphite), the two-dimensional (2D) single atomic carbon sheet of graphene has emerged as an attractive candidate for energy applications due to its unique structure and properties. Like other materials, however, a graphene-based material that possesses desirable bulk properties rarely features the surface characteristics...

Photoluminescence properties of graphene versus other carbon nanomaterials.

Abstract: Photoluminescent nanomaterials continue to garner research attention becauseof their many applications. For many years, researchers have focused on quantum dots (QDs) of semiconductor nanocrystals for their excellent performance and predictable fluorescence color variations that depend on the sizes of the nanocrystals. Even with these advantages, QDs can present some major limitations, such as the use of heavy metals in the high-performance semiconductor QDs. Therefore, researchers continue to be interested in developing new QDs or related nanomaterials. Recently, various nanoscale configurations of carbon have emerged as potential new platforms in the development of brightly photoluminescent materials.As a perfect π-conjugated single sheet, graphene lacks electronic bandgaps andis not photoluminescent. Therefore, researchers have created energy bandgaps within graphene as a strategy to impart fluorescence emissions. Researchers have explored many experimental techniques to introduce bandgaps, such as cut...

Ion conductivity and transport by porous coordination polymers and metal-organic frameworks.

Abstract: Ion conduction and transport in solids are both interesting and useful and are found in widely distinct materials, from those in battery-related technologies to those in biological systems. Scientists have approached the synthesis of ion-conductive compounds in a variety of ways, in the areas of organic and inorganic chemistry. Recently, based on their ion-conducting behavior, porous coordination polymers (PCPs) and metal–organic frameworks (MOFs) have been recognized for their easy design and the dynamic behavior of the ionic components in the structures. These PCP/MOFs consist of metal ions (or clusters) and organic ligands structured via coordination bonds. They could have highly concentrated mobile ions with dynamic behavior, and their characteristics have inspired the design of a new class of ion conductors and transporters.In this Account, we describe the state-of-the-art of studies of ion conductivity by PCP/MOFs and nonporous coordination polymers (CPs) and offer future perspectives. PCP/MOF struc...

The halogen bond in the design of functional supramolecular materials: recent advances.

Abstract: Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for molecular recognition and the design of functional materials. First, halogen bonds tend to be much more directional than (single) hydrogen bonds. Second, the interaction strength scales with the polarizability of the bond-donor atom, a feature that researchers can tune through single-atom mutation. In addition, halogen bonds are hydrophobic whereas hydrogen bonds are hydrophilic. Lastly, the size of the bond-donor atom (halogen) is significantly larger than hydrogen. As a result, halogen bonding provides supramolecular chemists with design tools that cannot be easily met with other types of noncovalent interactions and opens up unprecedented possibilities in the design of smart functional materials.This Account highlights the recent advances in the design of hal...

Materials for Microfluidic Chip Fabrication

Abstract: Through manipulating fluids using microfabricated channeland chamber structures, microfluidics is a powerful tool to realize high sensitive, high speed, high throughput, and low cost analysis. In addition, the method can establish a well-controlled microenivroment for manipulating fluids and particles. It also has rapid growing implementations in both sophisticated chemical/biological analysis and low-cost point-of-care assays. Some unique phenomena emerge at the micrometer scale. For example, reactions are completed in a shorter amount of time as the travel distances of mass and heat are relatively small; the flows are usually laminar; and the capillary effect becomes dominant owing to large surface-to-volume ratios. In the meantime, the surface properties of the device material are greatly amplified, which can lead to either unique functions or problems that we would not encounter at the macroscale. Also, each material inherently corresponds with specific microfabrication strategies and certain native p...

Understanding the Toxicity of Carbon Nanotubes

Abstract: Because of their unique physical, chemical, electrical, and mechanical properties, carbon nanotubes (CNTs) have attracted a great deal of research interest and have many potential applications. As large-scale production and application of CNTs increases, the general population is more likely to be exposed to CNTs either directly or indirectly, which has prompted considerable attention about human health and safety issues related to CNTs. Although considerable experimental data related to CNT toxicity at the molecular, cellular, and whole animal levels have been published, the results are often conflicting. Therefore, a systematic understanding of CNT toxicity is needed but has not yet been developed. In this Account, we highlight recent investigations into the basis of CNT toxicity carried out by our team and by other laboratories. We focus on several important factors that explain the disparities in the experimental results of nanotoxicity, such as impurities, amorphous carbon, surface charge, shape, length, agglomeration, and layer numbers. The exposure routes, including inhalation, intravenous injection, or dermal or oral exposure, can also influence the in vivo behavior and fate of CNTs. The underlying mechanisms of CNT toxicity include oxidative stress, inflammatory responses, malignant transformation, DNA damage and mutation (errors in chromosome number as well as disruption of the mitotic spindle), the formation of granulomas, and interstitial fibrosis. These findings provide useful insights for de novo design and safe application of carbon nanotubes and their risk assessment to human health. To obtain reproducible and accurate results, researchers must establish standards and reliable detection methods, use standard CNT samples as a reference control, and study the impact of various factors systematically. In addition, researchers need to examine multiple types of CNTs, different cell lines and animal species, multidimensional evaluation methods, and exposure conditions. To make results comparable among different institutions and countries, researchers need to standardize choices in toxicity testing such as that of cell line, animal species, and exposure conditions. The knowledge presented here should lead to a better understanding of the key factors that can influence CNT toxicity so that their unwanted toxicity might be avoided.

Evolution of Strategies for Modern Rechargeable Batteries

Abstract: This Account provides perspective on the evolution of the rechargeable battery and summarizes innovations in the development of these devices. Initially, I describe the components of a conventional rechargeable battery along with the engineering parameters that define the figures of merit for a single cell. In 1967, researchers discovered fast Na+ conduction at 300 K in Na β,β′′-alumina. Since then battery technology has evolved from a strongly acidic or alkaline aqueous electrolyte with protons as the working ion to an organic liquid-carbonate electrolyte with Li+ as the working ion in a Li-ion battery. The invention of the sodium-sulfur and Zebra batteries stimulated consideration of framework structures as crystalline hosts for mobile guest alkali ions, and the jump in oil prices in the early 1970s prompted researchers to consider alternative room-temperature batteries with aprotic liquid electrolytes. With the existence of Li primary cells and ongoing research on the chemistry of reversible Li interca...

High performance photovoltaic applications using solution-processed small molecules.

Abstract: Energy remains a critical issue for the survival and prosperity of humancivilization. Many experts believe that the eventual solution for sustainable energy is the use of direct solar energy as the main energy source. Among the options for renewable energy, photovoltaic technologies that harness solar energy offer a way to harness an unlimited resource and minimum environment impact in contrast with other alternatives such as water, nuclear, and wind energy.Currently, almost all commercial photovoltaic technologies use Si-based technology, which has a number of disadvantages including high cost, lack of flexibility, and the serious environmental impact of the Si industry. Other technologies, such as organic photovoltaic (OPV) cells, can overcome some of these issues. Today, polymer-based OPV (P-OPV) devices have achieved power conversion efficiencies (PCEs) that exceed 9%. Compared with P-OPV, small molecules based OPV (SM-OPV) offers further advantages, including a defined structure for more reproducible...

Physicochemical properties determine nanomaterial cellular uptake, transport and fate

Abstract: Although a growing number of innovations have emerged in the fields of nanobiotechnology and nanomedicine, new engineered nanomaterials (ENMs) with novel physicochemical properties are posing novel challenges to understand the full spectrum of interactions at the nano–bio interface. Because these could include potentially hazardous interactions, researchers need a comprehensive understanding of toxicological properties of nanomaterials and their safer design. In depth research is needed to understand how nanomaterial properties influence bioavailability, transport, fate, cellular uptake, and catalysis of injurious biological responses. Toxicity of ENMs differ with their size and surface properties, and those connections hold true across a spectrum of in vitro to in vivo nano–bio interfaces. In addition, the in vitro results provide a basis for modeling the biokinetics and in vivo behavior of ENMs. Nonetheless, we must use caution in interpreting in vitro toxicity results too literally because of dosimetry...

Nanotechnology for a safe and sustainable water supply: enabling integrated water treatment and reuse.

Abstract: Ensuring reliable access to clean and affordable water is one of the greatest global challenges of this century. As the world’s population increases, water pollution becomes more complex and difficult to remove, and global climate change threatens to exacerbate water scarcity in many areas, the magnitude of this challenge is rapidly increasing. Wastewater reuse is becoming a common necessity, even as a source of potable water, but our separate wastewater collection and water supply systems are not designed to accommodate this pressing need. Furthermore, the aging centralized water and wastewater infrastructure in the developed world faces growing demands to produce higher quality water using less energy and with lower treatment costs. In addition, it is impractical to establish such massive systems in developing regions that currently lack water and wastewater infrastructure. These challenges underscore the need for technological innovation to transform the way we treat, distribute, use, and reuse water t...

Shape-Controlled Synthesis of Pd Nanocrystals and Their Catalytic Applications

Abstract: Palladium is a marvelous catalyst for a rich variety of reactions in industrial processes and commercial devices. Most Pd-catalyzed reactions exhibit structure sensitivity, meaning that the activity or selectivity depends on the arrangement of atoms on the surface. Previously, such reactions could only be studied in ultrahigh vacuum using Pd single crystals cut with a specific crystallographic plane. However, these model catalysts are far different from real catalytic systems owing to the absence of atoms at corners and edges and the extremely small specific surface areas for the model systems. Indeed, enhancing the performance of a Pd-based catalyst, in part to reduce the amount needed of this precious and rare metal for a given reaction, requires the use of Pd with the highest possible specific surface area. Recent advances in nanocrystal synthesis are offering a great opportunity to investigate and quantify the structural sensitivity of catalysts based on Pd and other metals. For a structure-sensitive reaction, the catalytic properties of Pd nanocrystals are strongly dependent on both the size and shape. The shape plays a more significant role in controlling activity and selectivity, because the shape controls not only the facets but also the proportions of surface atoms at corners, edges, and planes, which affect the outcomes of possible reactions. We expect catalysts based on Pd nanocrystals with optimized shapes to meet the increasing demands of industrial applications at reduced loadings and costs. In this Account, we discuss recent advances in the synthesis of Pd nanocrystals with controlled shapes and their resulting performance as catalysts for a large number of reactions. First, we review various synthetic strategies based on oxidative etching, surface capping, and kinetic control that have been used to direct the shapes of nanocrystals. When crystal growth is under thermodynamic control, the capping agent plays a pivotal role in determining the shape of a product by altering the order of surface energies for different facets through selective adsorption; the resulting product has the lowest possible total surface energy. In contrast, the product of a kinetically controlled synthesis often deviates from the thermodynamically favored structure, with notable examples including nanocrystals enclosed by high-index facets or concave surfaces. We then discuss the key parameters that control the nucleation and growth of Pd nanocrystals to decipher potential growth mechanisms and build a connection between the experimental conditions and the pathways to different shapes. Finally, we present a number of examples to highlight the use of these Pd nanocrystals as catalysts or electrocatalysts for various applications with structure-sensitive properties. We believe that a deep understanding of the shape-dependent catalytic properties, together with an ability to experimentally maneuver the shape of metal nanocrystals, will eventually lead to rational design of advanced catalysts with substantially enhanced performance.

Fate and Risks of Nanomaterials in Aquatic and Terrestrial Environments

Abstract: Over the last decade, nanoparticles have been used more frequently in industrial applications and in consumer and medical products, and these applications of nanoparticles will likely continue to increase. Concerns about the environmental fate and effects of these materials have stimulated studies to predict environmental concentrations in air, water, and soils and to determine threshold concentrations for their ecotoxicological effects on aquatic or terrestrial biota.Nanoparticles can be added to soils directly in fertilizers orplant protection products or indirectly through application to land or wastewater treatment products such as sludges or biosolids. Nanoparticles may enter aquatic systems directly through industrial discharges or from disposal of wastewater treatment effluents or indirectly through surface runoff from soils. Researchers have used laboratory experiments to begin to understand the effects of nanoparticles on waters and soils, and this Account reviews that research and the translatio...

Exploiting the Reversible Covalent Bonding of Boronic Acids: Recognition, Sensing, and Assembly

Abstract: Boronic acids can interact with Lewis bases to generate boronate anions, and they can also bind with diol units to form cyclic boronate esters. Boronic acid based receptor designs originated when L...