Showing papers in "ChemInform in 2016"

Direct Capture of CO2 from Ambient Air

Abstract: The increase in the global atmospheric CO2 concentration resulting from over a century of combustion of fossil fuels has been associated with significant global climate change. With the global population increase driving continued increases in fossil fuel use, humanity’s primary reliance on fossil energy for the next several decades is assured. Traditional modes of carbon capture such as precombustion and postcombustion CO2 capture from large point sources can help slow the rate of increase of the atmospheric CO2 concentration, but only the direct removal of CO2 from the air, or “direct air capture” (DAC), can actually reduce the global atmospheric CO2 concentration. The past decade has seen a steep rise in the use of chemical sorbents that are cycled through sorption and desorption cycles for CO2 removal from ultradilute gases such as air. This Review provides a historical overview of the field of DAC, along with an exhaustive description of the use of chemical sorbents targeted at this application. Solv...

Inorganic Solid‐State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction

Abstract: Citation Bachman, John Christopher, Sokseiha Muy, Alexis Grimaud, Hao-Hsun Chang, Nir Pour, Simon F. Lux, Odysseas Paschos, et al. “Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction.” Chemical Reviews 116, no. 1 (January 13, 2016): 140–162. As Published http://dx.doi.org/10.1021/acs.chemrev.5b00563 Publisher American Chemical Society (ACS)

Review on Research Achievements of Biogas from Anaerobic Digestion

Abstract: With the rising demand for renewable energy and environmental protection, anaerobic digestion of biogas technology has attracted considerable attention within the scientific community. This paper presents a comprehensive review of research achievements on anaerobic digestion developments for biogas production. The review includes a discussion of factors affecting efficiency (temperature, pH, C/N ratio, OLR and retention time), accelerants (greenery biomass, biological pure culture and inorganic additives), reactors (conventional anaerobic reactors, sludge retention reactors and anaerobic membrane reactors) and biogas AD processes (lignocellulose waste, municipal solid waste, food waste, livestock manure and waste activated sludge) based on substrate characteristics and discusses the application of each forementioned aspect. The factors affecting efficiency are crucial to anaerobic digestion, because they play a major role in biogas production and determine the metabolic conditions for microorganism growth. As an additive, an accelerant is not only regarded as a nutrient resource, but can also improve biodegradability. The focus of reactor design is the sufficient utilization of a substrate by changing the feeding method and enhancing the attachment to biomass. The optimal digestion process balances the optimal digest conditions with the cost-optimal input/output ratio. Additionally, establishment of theoretical and technological studies should emphasize practicality based on laboratory-scale experiments because further development of biogas plants would allow for a transition from household to medium- and large-scale projects; therefore, improving stability and efficiency are recommended for advancing AD research.

Lignocellulosic Biomass Pyrolysis: A Review of Product Properties and Effects of Pyrolysis Parameters

Abstract: Pyrolysis is one of the thermochemical technologies for converting biomass into energy and chemical products consisting of liquid bio-oil, solid biochar, and pyrolytic gas. Depending on the heating rate and residence time, biomass pyrolysis can be divided into three main categories slow (conventional), fast and flash pyrolysis mainly aiming at maximising either the bio-oil or biochar yields. Synthesis gas or hydrogen-rich gas can also be the target of biomass pyrolysis. Maximised gas rates can be achieved through the catalytic pyrolysis process, which is now increasingly being developed. Biomass pyrolysis generally follows a three-step mechanism comprising of dehydration, primary and secondary reactions. Dehydrogenation, depolymerisation, and fragmentation are the main competitive reactions during the primary decomposition of biomass. A number of parameters affect the biomass pyrolysis process, yields and properties of products. These include the biomass type, biomass pretreatment (physical, chemical, and biological), reaction atmosphere, temperature, heating rate and vapour residence time. This manuscript gives a general summary of the properties of the pyrolytic products and their analysis methods. Also provided are a review of the parameters that affect biomass pyrolysis and a summary of the state of industrial pyrolysis technologies.

A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications.

Abstract: Despite the remarkable rise in efficiencies of solar cells containing the lead-halide perovskite absorbers RPbX3 (R = organic cation; X = Br– or I–), the toxicity of lead remains a concern for the large-scale implementation of this technology. This has spurred the search for lead-free materials with similar optoelectronic properties. Here, we use the double-perovskite structure to incorporate nontoxic Bi3+ into the perovskite lattice in Cs2AgBiBr6 (1). The solid shows a long room-temperature fundamental photoluminescence (PL) lifetime of ca. 660 ns, which is very encouraging for photovoltaic applications. Comparison between single-crystal and powder PL decay curves of 1 suggests inherently high defect tolerance. The material has an indirect bandgap of 1.95 eV, suited for a tandem solar cell. Furthermore, 1 is significantly more heat and moisture stable compared to (MA)PbI3. The extremely promising optical and physical properties of 1 shown here motivate further exploration of both inorganic and hybrid hal...

Photoredox Catalysis in Organic Chemistry

Abstract: In recent years, photoredox catalysis has come to the forefront in organic chemistry as a powerful strategy for the activation of small molecules. In a general sense, these approaches rely on the ability of metal complexes and organic dyes to convert visible light into chemical energy by engaging in single-electron transfer with organic substrates, thereby generating reactive intermediates. In this Perspective, we highlight the unique ability of photoredox catalysis to expedite the development of completely new reaction mechanisms, with particular emphasis placed on multicatalytic strategies that enable the construction of challenging carbon–carbon and carbon–heteroatom bonds.

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis

Abstract: Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple "upstream" (i.e., lignin bioengineering, lignin isolation and "early-stage catalytic conversion of lignin") and "downstream" (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a "beginning-to-end" analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on the improved understanding of lignin's biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.

Photochemical Route for Synthesizing Atomically Dispersed Palladium Catalysts.

Abstract: Stable atomically dispersed Pd catalyst particles on ethylene glycolate (EG)-stabilized ultrathin TiO2 nanosheet supports (Pd ≤1.5%) are prepared by UV irradiation (Xe lamp) of an aqueous suspension of two-atom-thick TiO2 nanosheets and H2PdCl4.

Evidence for Hydrodynamic Electron Flow in PdCoO2.

Abstract: Electron transport is conventionally determined by the momentum-relaxing scattering of electrons by the host solid and its excitations. Hydrodynamic fluid flow through channels, in contrast, is determined partly by the viscosity of the fluid, which is governed by momentum-conserving internal collisions. A long-standing question in the physics of solids has been whether the viscosity of the electron fluid plays an observable role in determining the resistance. We report experimental evidence that the resistance of restricted channels of the ultrapure two-dimensional metal palladium cobaltate (PdCoO2) has a large viscous contribution. Comparison with theory allows an estimate of the electronic viscosity in the range between 6 × 10–3 kg m–1 s–1 and 3 × 10–4 kg m–1 s–1, versus 1 × 10–3 kg m–1 s–1 for water at room temperature.

Transition‐Metal (Co, Ni, and Fe)‐Based Electrocatalysts for the Water Oxidation Reaction

Abstract: Increasing energy demands and environment awareness have promoted extensive research on the development of alternative energy conversion and storage technologies with high efficiency and environmental friendliness. Among them, water splitting is very appealing, and is receiving more and more attention. The critical challenge of this renewable-energy technology is to expedite the oxygen evolution reaction (OER) because of its slow kinetics and large overpotential. Therefore, developing efficient electrocatalysts with high catalytic activities is of great importance for high-performance water splitting. In the past few years, much effort has been devoted to the development of alternative OER electrocatalysts based on transition-metal elements that are low-cost, highly efficient, and have excellent stability. Here, recent progress on the design, synthesis, and application of OER electrocatalysts based on transition-metal elements, including Co, Ni, and Fe, is summarized, and some invigorating perspectives on the future developments are provided.

Using Carbon Dioxide as a Building Block in Organic Synthesis

Abstract: Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon--trapped in a waste product--and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO₂ and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources.

2D Transition‐Metal‐Dichalcogenide‐Nanosheet‐Based Composites for Photocatalytic and Electrocatalytic Hydrogen Evolution Reactions

Abstract: Hydrogen (H2) is one of the most important clean and renewable energy sources for future energy sustainability. Nowadays, photocatalytic and electrocatalytic hydrogen evolution reactions (HERs) from water splitting are considered as two of the most efficient methods to convert sustainable energy to the clean energy carrier, H2. Catalysts based on transition metal dichalcogenides (TMDs) are recognized as greatly promising substitutes for noble-metal-based catalysts for HER. The photocatalytic and electrocatalytic activities of TMD nanosheets for the HER can be further improved after hybridization with many kinds of nanomaterials, such as metals, oxides, sulfides, and carbon materials, through different methods including the in situ reduction method, the hot-injection method, the heating-up method, the hydro(solvo)thermal method, chemical vapor deposition (CVD), and thermal annealing. Here, recent progress in photocatalytic and electrocatalytic HERs using 2D TMD-based composites as catalysts is discussed.

Towards Lignin-Based Functional Materials in a Sustainable World

Abstract: In light of the incessant consumption of raw materials in the world today, the search for sustainable resources is ever pressing. Lignin, the second most naturally abundant biomass, which makes up 15% to 35% of the cell walls of terrestrial plants, has always been treated as waste and used in low-value applications such as heat and electricity generation. However, its abundance in nature could potentially solve the problem of the rapidly depleting resources if it was successfully translated into a renewable resource or valorized to higher value materials. Advanced lignin modification chemistry has generated a number of functional lignin-based polymers, which integrate both the intrinsic features of lignin and additional properties of the grafted polymers. These modified lignin and its copolymers display better miscibility with other polymeric matrices, leading to improved performance for these lignin/polymer composites. This review summarizes the progress in using such biopolymers as reinforcement fillers, antioxidants, UV adsorbents, antimicrobial agents, carbon precursors and biomaterials for tissue engineering and gene therapy. Recent developments in lignin-based smart materials are discussed as well.

Cu and Cu‐Based Nanoparticles: Synthesis and Applications in Catalysis

Abstract: The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications i...

Functionalized Hexagonal Boron Nitride Nanomaterials: Emerging Properties and Applications

Abstract: Functionalization is an important way to breed new properties and applications for a material. This review presents an overview of the progresses in functionalized hexagonal boron nitride (h-BN) nanomaterials. It begins with an introduction of h-BN structural features, physical and chemical properties, followed by an emphasis on the developments of BN functionalization strategies and its emerging properties/applications, and ends with the research perspectives. Different functionalization methods, including physical and chemical routes, are comprehensively described toward fabrication of various BN derivatives, hetero- and porous structures, etc. Novel properties of functionalized BN materials, such as high water solubility, excellent biocompatibility, tunable surface affinities, good processibility, adjustable band gaps, etc., have guaranteed wide applications in biomedical, electronic, composite, environmental and "green" energy-related fields.

Counting on Natural Products for Drug Design

Abstract: Natural products and their molecular frameworks have a long tradition as valuable starting points for medicinal chemistry and drug discovery. Recently, there has been a revitalization of interest in the inclusion of these chemotypes in compound collections for screening and achieving selective target modulation. Here we discuss natural-product-inspired drug discovery with a focus on recent advances in the design of synthetically tractable small molecules that mimic nature's chemistry. We highlight the potential of innovative computational tools in processing structurally complex natural products to predict their macromolecular targets and attempt to forecast the role that natural-product-derived fragments and fragment-like natural products will play in next-generation drug discovery.

“Water‐in‐Salt” Electrolyte Enables High‐Voltage Aqueous Lithium‐Ion Chemistries.

Abstract: Highly concentrated aqueous solutions of LiN(SO2CF3)2 (5—20 M at 25 °C) are used as an electrolyte in a CR2032-type coin cell containing either LiMn2O4 or LiNi0.8Co0.15Al0.05O2 as the cathode and Cu-leached Mo6S8 Chevrel phase as the anode separated by glass fiber fabrics.

Oxygen Evolution Reaction Electrocatalysis on Transition Metal Oxides and (Oxy)hydroxides: Activity Trends and Design Principles

Abstract: Poor oxygen evolution reaction (OER) catalysis limits the efficiency of H2 production from water electrolysis and photoelectrolysis routes to large-scale energy storage. Despite nearly a century of research, the factors governing the activity of OER catalysts are not well understood. In this Perspective, we discuss recent advances in understanding the OER in alkaline media for earth-abundant, first-row, transition-metal oxides and (oxy)hydroxides. We argue that the most-relevant structures for study are thermodynamically stable (oxy)hydroxides and not crystalline oxides. We discuss thin-film electrochemical microbalance techniques to accurately quantify intrinsic activity and in situ conductivity measurements to identify materials limited by electronic transport. We highlight the dramatic effect that Fe cations—added either intentionally or unintentionally from ubiquitous electrolyte impurities—have on the activity of common OER catalysts. We find new activity trends across the first-row transition metals...

Atomically Thin Two‐Dimensional Organic‐Inorganic Hybrid Perovskites.

Abstract: Atomically thin sheets of the hybrid perovskite (BuNH3)2PbBr4 are grown on Si/SiO2 substrates by evaporation of a highly diluted stoichiometric solution of MeNH3Br and PbCl2 in anhydrous DMF/PhCl (1:1) (75 °C, 10 min).

Hydrogels Based on Cellulose and Chitin: Fabrication, Properties, and Applications

Abstract: This review is focused on the fabrication, properties, and applications of hydrogels prepared from two of the most abundant biopolymers on earth, cellulose and chitin. The review emphasizes the latest developments in hydrogel preparation (including solvent systems, cross-linker types, and preparation methods, which determine the “greenness” of the process) using these biocompatible and biodegradable biopolymers. The preparation of both physical (without covalent cross-links) and chemical (with covalent cross-links) hydrogels via dissolution/gelation is discussed. Additionally, formation of injectable thermoset and/or pH sensitive hydrogels from aqueous solutions of derivatives (chitosan, methyl cellulose, and hydroxypropylmethyl cellulose) with or without a cross-linker are discussed. This review also compares the design parameters for different applications of various pure and composite hydrogels based on cellulose, chitin, or chitosan, including applications as controlled and targeted drug delivery systems, improved tissue engineering scaffolds, wound dressings, water purification sorbents, and others.

In vivo Delivery, Pharmacokinetics, Biodistribution and Toxicity of Iron Oxide Nanoparticles

Abstract: Iron oxide nanoparticles (IONPs) have been extensively used during the last two decades, either as effective bio-imaging contrast agents or as carriers of biomolecules such as drugs, nucleic acids and peptides for controlled delivery to specific organs and tissues. Most of these novel applications require elaborate tuning of the physiochemical and surface properties of the IONPs. As new IONPs designs are envisioned, synergistic consideration of the body's innate biological barriers against the administered nanoparticles and the short and long-term side effects of the IONPs become even more essential. There are several important criteria (e.g. size and size-distribution, charge, coating molecules, and plasma protein adsorption) that can be effectively tuned to control the in vivo pharmacokinetics and biodistribution of the IONPs. This paper reviews these crucial parameters, in light of biological barriers in the body, and the latest IONPs design strategies used to overcome them. A careful review of the long-term biodistribution and side effects of the IONPs in relation to nanoparticle design is also given. While the discussions presented in this review are specific to IONPs, some of the information can be readily applied to other nanoparticle systems, such as gold, silver, silica, calcium phosphates and various polymers.

Catalysis of Radical Reactions: A Radical Chemistry Perspective

Abstract: The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in "catalytic amounts" is a catalyst, an initiator, or something else? Herein we critically address both catalyst-free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non-chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.

Emerging Frontiers in Drug Delivery

Abstract: Medicine relies on the use of pharmacologically active agents (drugs) to manage and treat disease. However, drugs are not inherently effective; the benefit of a drug is directly related to the manner by which it is administered or delivered. Drug delivery can affect drug pharmacokinetics, absorption, distribution, metabolism, duration of therapeutic effect, excretion, and toxicity. As new therapeutics (e.g., biologics) are being developed, there is an accompanying need for improved chemistries and materials to deliver them to the target site in the body, at a therapeutic concentration, and for the required period of time. In this Perspective, we provide an historical overview of drug delivery and controlled release followed by highlights of four emerging areas in the field of drug delivery: systemic RNA delivery, drug delivery for localized therapy, oral drug delivery systems, and biologic drug delivery systems. In each case, we present the barriers to effective drug delivery as well as chemical and mater...

Organic Photoredox Catalysis

Abstract: In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.

Forging Colloidal Nanostructures via Cation Exchange Reactions

Abstract: Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field.

Radicals: Reactive Intermediates with Translational Potential

Abstract: This Perspective illustrates the defining characteristics of free radical chemistry, beginning with its rich and storied history. Studies from our laboratory are discussed along with recent developments emanating from others in this burgeoning area. The practicality and chemoselectivity of radical reactions enable rapid access to molecules of relevance to drug discovery, agrochemistry, material science, and other disciplines. Thus, these reactive intermediates possess inherent translational potential, as they can be widely used to expedite scientific endeavors for the betterment of humankind.

Methods and Strategies for the Synthesis of Diverse Nanoparticles and Their Applications: A Comprehensive Overview

Abstract: Ongoing advances in nanotechnology research have established a variety of methods to synthesize nanoparticles (NPs) from a diverse range of materials, including metals, semiconductors, ceramics, metal oxides, polymers, etc. Depending upon their origin and synthesis methods, NPs possess unique physicochemical, structural and morphological characteristics, which are important in a wide variety of applications concomitant to electronic, optoelectronic, optical, electrochemical, environment and biomedical fields. This review provides a comprehensive overview on various physical, chemical and bio-assisted methods largely employed to synthesize and fabricate NPs of varying size, surface characteristics, functionalities and physicochemical behavior. The key applications of nanoparticles have also been discussed.

Direct Alkylation of Heteroarenes with Unactivated Bromoalkanes Using Photoredox Gold Catalysis.

Abstract: Although visible light photoredox catalysis has emerged as a powerful tool for the construction of C–C bonds, common catalysts and/or their photoexcited states suffer from low redox potentials, limiting their applicability to alkyl radical generation from substrates with activated carbon–halogen bonds. Radicals derived from these activated compounds, being highly electrophilic or stabilized, do not undergo efficient addition to heteroarenes. Herein we describe the photocatalytic generation of nucleophilic alkyl radicals from unactivated bromoalkanes as part of a universal and efficient cross-coupling strategy for the direct alkylation of heteroarenes using a dimeric gold(I) photoredox catalyst, [Au2(bis(diphenylphosphino)methane)2]Cl2. The method proves to be efficient for alkylation of arenes under mild conditions in the absence of directing groups.