Showing papers in "Chemical Reviews in 2007"

Conjugated polymer-based organic solar cells

Abstract: The need to develop inexpensive renewable energy sources stimulates scientific research for efficient, low-cost photovoltaic devices.1 The organic, polymer-based photovoltaic elements have introduced at least the potential of obtaining cheap and easy methods to produce energy from light.2 The possibility of chemically manipulating the material properties of polymers (plastics) combined with a variety of easy and cheap processing techniques has made polymer-based materials present in almost every aspect of modern society.3 Organic semiconductors have several advantages: (a) lowcost synthesis, and (b) easy manufacture of thin film devices by vacuum evaporation/sublimation or solution cast or printing technologies. Furthermore, organic semiconductor thin films may show high absorption coefficients4 exceeding 105 cm-1, which makes them good chromophores for optoelectronic applications. The electronic band gap of organic semiconductors can be engineered by chemical synthesis for simple color changing of light emitting diodes (LEDs).5 Charge carrier mobilities as high as 10 cm2/V‚s6 made them competitive with amorphous silicon.7 This review is organized as follows. In the first part, we will give a general introduction to the materials, production techniques, working principles, critical parameters, and stability of the organic solar cells. In the second part, we will focus on conjugated polymer/fullerene bulk heterojunction solar cells, mainly on polyphenylenevinylene (PPV) derivatives/(1-(3-methoxycarbonyl) propyl-1-phenyl[6,6]C61) (PCBM) fullerene derivatives and poly(3-hexylthiophene) (P3HT)/PCBM systems. In the third part, we will discuss the alternative approaches such as polymer/polymer solar cells and organic/inorganic hybrid solar cells. In the fourth part, we will suggest possible routes for further improvements and finish with some conclusions. The different papers mentioned in the text have been chosen for didactical purposes and cannot reflect the chronology of the research field nor have a claim of completeness. The further interested reader is referred to the vast amount of quality papers published in this field during the past decade.

Chemical Routes for the Transformation of Biomass into Chemicals

Abstract: 3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical sensors based on amplifying fluorescent conjugated polymers.

Abstract: The field of chemical sensing is becoming ever more dependent upon novel materials. Polymers, crystals, glasses, particles, and nanostructures have made a profound impact and have endowed modern sensory systems with superior performance. Electronic polymers have emerged as one of the most important classes of transduction materials; they readily transform a chemical signal into an easily measured electrical or optical event. Although our group reviewed this field in 2000,1 the high levels of activity and the impact of these methods now justify a subsequent review as part of this special issue. In this review we restrict our discussions to purely fluorescence-based methods using conjugated polymers (CPs). We further confine our detailed coverage to articles published since our previous review and will only detail earlier research in this Introduction to illustrate fundamental concepts and terminology that underpin the recent literature.

Charge transport in organic semiconductors.

Abstract: 2.2. Materials 929 2.3. Factors Influencing Charge Mobility 931 2.3.1. Molecular Packing 931 2.3.2. Disorder 932 2.3.3. Temperature 933 2.3.4. Electric Field 934 2.3.5. Impurities 934 2.3.6. Pressure 934 2.3.7. Charge-Carrier Density 934 2.3.8. Size/molecular Weight 935 3. The Charge-Transport Parameters 935 3.1. Electronic Coupling 936 3.1.1. The Energy-Splitting-in-Dimer Method 936 3.1.2. The Orthogonality Issue 937 3.1.3. Impact of the Site Energy 937 3.1.4. Electronic Coupling in Oligoacene Derivatives 938

Aryl-aryl bond formation by transition-metal-catalyzed direct arylation.

Abstract: The biaryl structural motif is a predominant feature in many pharmaceutically relevant and biologically active compounds. As a result, for over a century 1 organic chemists have sought to develop new and more efficient aryl -aryl bond-forming methods. Although there exist a variety of routes for the construction of aryl -aryl bonds, arguably the most common method is through the use of transition-metalmediated reactions. 2-4 While earlier reports focused on the use of stoichiometric quantities of a transition metal to carry out the desired transformation, modern methods of transitionmetal-catalyzed aryl -aryl coupling have focused on the development of high-yielding reactions achieved with excellent selectivity and high functional group tolerance under mild reaction conditions. Typically, these reactions involve either the coupling of an aryl halide or pseudohalide with an organometallic reagent (Scheme 1), or the homocoupling of two aryl halides or two organometallic reagents. Although a number of improvements have developed the former process into an industrially very useful and attractive method for the construction of aryl -aryl bonds, the need still exists for more efficient routes whereby the same outcome is accomplished, but with reduced waste and in fewer steps. In particular, the obligation to use coupling partners that are both activated is wasteful since it necessitates the installation and then subsequent disposal of stoichiometric activating agents. Furthermore, preparation of preactivated aryl substrates often requires several steps, which in itself can be a time-consuming and economically inefficient process.

Transformation of carbon dioxide.

Abstract: 4.3. Reaction Mechanism 2373 4.4. Asymmetric Synthesis 2374 4.5. Outlook 2374 5. Alternating Polymerization of Oxiranes and CO2 2374 5.1. Reaction Outlines 2374 5.2. Catalyst 2376 5.3. Asymmetric Polymerization 2377 5.4. Immobilized Catalysts 2377 6. Synthesis of Urea and Urethane Derivatives 2378 7. Synthesis of Carboxylic Acid 2379 8. Synthesis of Esters and Lactones 2380 9. Synthesis of Isocyanates 2382 10. Hydrogenation and Hydroformylation, and Alcohol Homologation 2382

Scientific aspects of polymer electrolyte fuel cell durability and degradation.

Abstract: Rod Borup is a Team Leader in the fuel cell program at Los Alamos National Lab in Los Alamos, New Mexico. He received his B.S.E. in Chemical Engineering from the University of Iowa in 1988 and his Ph.D. from the University of Washington in 1993. He has worked on fuel cell technology since 1994, working in the areas of hydrogen production and PEM fuel cell stack components. He has been awarded 12 U.S. patents, authored over 40 papers related to fuel cell technology, and presented over 50 oral papers at national meetings. His current main research area is related to water transport in PEM fuel cells and PEM fuel cell durability. Recently, he was awarded the 2005 DOE Hydrogen Program R&D Award for the most significant R&D contribution of the year for his team's work in fuel cell durability and was the Principal Investigator for the 2004 Fuel Cell Seminar (San Antonio, TX, USA) Best Poster Award. Jeremy Meyers is an Assistant Professor of materials science and engineering and mechanical engineering at the University of Texas at Austin, where his research focuses on the development of electrochemical energy systems and materials. Prior to joining the faculty at Texas, Jeremy workedmore » as manager of the advanced transportation technology group at UTC Power, where he was responsible for developing new system designs and components for automotive PEM fuel cell power plants. While at UTC Power, Jeremy led several customer development projects and a DOE-sponsored investigation into novel catalysts and membranes for PEM fuel cells. Jeremy has coauthored several papers on key mechanisms of fuel cell degradation and is a co-inventor of several patents. In 2006, Jeremy and several colleagues received the George Mead Medal, UTC's highest award for engineering achievement, and he served as the co-chair of the Gordon Research Conference on fuel cells. Jeremy received his Ph.D. in Chemical Engineering from the University of California at Berkeley and holds a Bachelor's Degree in Chemical Engineering from Stanford University. Bryan Pivovar received his B.S. in Chemical Engineering from the University of Wisconsin in 1994. He completed his Ph.D. in Chemical Engineering at the University of Minnesota in 2000 under the direction of Profs. Ed Cussler and Bill Smyrl, studying transport properties in fuel cell electrolytes. He continued working in the area of polymer electrolyte fuel cells at Los Alamos National Laboratory as a post-doc (2000-2001), as a technical staff member (2001-2005), and in his current position as a team leader (2005-present). In this time, Bryan's research has expanded to include further aspects of fuel cell operation, including electrodes, subfreezing effects, alternative polymers, hydroxide conductors, fuel cell interfaces, impurities, water transport, and high-temperature membranes. Bryan has served at various levels in national and international conferences and workshops, including organizing a DOE sponsored workshop on freezing effects in fuel cells and an ARO sponsored workshop on alkaline membrane fuel cells, and he was co-chair of the 2007 Gordon Research Conference on Fuel Cells. Minoru Inaba is a Professor at the Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University, Japan. He received his B.Sc. from the Faculty of Engineering, Kyoto University, in 1984 and his M.Sc. in 1986 and his Dr. Eng. in 1995 from the Graduate School of Engineering, Kyoto University. He has worked on electrochemical energy conversion systems including fuel cells and lithium-ion batteries at Kyoto University (1992-2002) and at Doshisha University (2002-present). His primary research interest is the durability of polymer electrolyte fuel cells (PEFCs), in particular, membrane degradation, and he has been involved in NEDO R&D research projects on PEFC durability since 2001. He has authored over 140 technical papers and 30 review articles. Kenichiro Ota is a Professor of the Chemical Energy Laboratory at the Graduate School of Engineering, Yokohama National University, Japan. He received his B.S.E. in Applied Chemistry from the University of Tokyo in 1968 and his Ph.D. from the University of Tokyo in 1973. He has worked on hydrogen energy and fuel cells since 1974, working on materials science for fuel cells and water electrolysis. He has published more than 150 original papers, 70 review papers, and 50 scientific books. He is now the president of the Hydrogen Energy Systems Society of Japan, the chairman of the Fuel Cell Research Group of the Electrochemical Society of Japan, and the chairman of the National Committee for the Standardization of the Stationary Fuel Cells. ABSTRACT TRUNCATED« less

Gold-Catalyzed Organic Reactions

Abstract: Although homogeneous gold catalysis was known previously, an exponential growth was only induced 12 years ago. The key findings which induce that rise of the field are discussed. This includes early reactions of allenes and furanynes and intermediates of these conversions as well as hydroarylation reactions. Other substrate types addressed are alkynyl epoxides and N-propargyl carboxamides. Important vinylgold intermediates, the transmetalation from gold to other transition metals, the development of new ligands for gold catalysis, and significant contributions from computational chemistry are other crucial points for the field highlighted here.

The Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry†

Abstract: 3.7. Palladium Nanoparticles as Catalysts 888 3.8. Other Transition-Metal Complexes 888 3.9. Transition-Metal-Free Reactions 889 4. Applications 889 4.1. Alkynylation of Arenes 889 4.2. Alkynylation of Heterocycles 891 4.3. Synthesis of Enynes and Enediynes 894 4.4. Synthesis of Ynones 896 4.5. Synthesis of Carbocyclic Systems 897 4.6. Synthesis of Heterocyclic Systems 898 4.7. Synthesis of Natural Products 903 4.8. Synthesis of Electronic and Electrooptical Molecules 906

Interparticle Coupling Effect on the Surface Plasmon Resonance of Gold Nanoparticles: From Theory to Applications

Abstract: 12.2.2. Four-Wave Mixing (FWM) 4849 12.2.3. Dye Aggregation 4850 12.2.4. Optoelectronic Nanodevices 4850 12.3. Sensor 4851 12.3.1. Chemical Sensor 4851 12.3.2. Biological Sensor 4851 12.4. Catalysis 4852 13. Conclusion and Perspectives 4852 14. Abbreviations 4853 15. Acknowledgements 4854 16. References 4854 * Corresponding author E-mail: tpal@chem.iitkgp.ernet.in. † Raidighi College. § Indian Institute of Technology. 4797 Chem. Rev. 2007, 107, 4797−4862

Organocatalysis by N-Heterocyclic Carbenes

Abstract: In the investigation of efficient chemical transformations, the carbon-carbon bond-forming reactions play an outstanding role. In this context, organocatalytic processes have achieved considerable attention. 1 Beside their facile reaction course, selectivity, and environmental friendliness, new synthetic strategies are made possible. Particularly, the inversion of the classical reactivity (Umpolung) opens up new synthetic pathways. 2 In nature, the coenzyme thiamine (vitamin B1), a natural thiazolium salt, utilizes a catalytic variant of this concept in biochemical processes as nucleophilic acylations. 3 The catalytically active species is a nucleophilic carbene. 4

Proton-Coupled Electron Transfer

Abstract: ▪ Abstract Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several are...

Catalysis in ionic liquids

Abstract: 2.5. Stabilization of IL Emulsions by Nanoparticles 2623 3. Hydrogenations in ILs 2623 3.1. Hydrogenation on IL-Stabilized Nanoparticles 2623 3.1.1. Hydrogenation of 1,3-Butadiene 2623 3.1.2. Hydrogenation of Alkenes and Arenes 2624 3.1.3. Hydrogenation of Ketones 2624 3.2. Homogeneous Catalytic Hydrogenation in ILs 2624 3.3. Hydrogenation of Functionalized ILs 2625 3.3.1. Selective Hydrogenation of Polymers 2625 3.4. Asymmetric Hydrogenations 2626 3.4.1. Enantioselective Hydrogenation 2626 3.5. Role of the ILs Purity in Hydrogenation Reactions 2628

Carbon-Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts

Abstract: 4.4. Pd on Modified Silica 159 4.5. Pd on Clay and Other Inorganic Materials 159 5. Stille, Fukuyama, and Negishi Reactions 159 5.1. Stille Reactions 159 5.1.1. Pd on Carbon (Pd/C) 159 5.1.2. Palladium on KF/Al2O3 159 5.1.3. Pd on Modified Silica (SiO2/TEG/Pd) 159 5.2. Fukuyama Reactions 159 5.2.1. Pd on Carbon (Pd/C) 159 5.2.2. Pd(OH)2 on Carbon (Perlman’s Catalyst) 160 5.3. Pd/C-Catalyzed Negishi Reactions 160 6. Ullmann-Type Coupling Reactions 161 6.1. Pd/C-Catalyzed Aryl−Aryl Coupling 161 6.2. Pd/C-Catalyzed Homocoupling of Vinyl Halides 162

Complex hydrides for hydrogen storage.

Abstract: Note: Times Cited: 875 Reference EPFL-ARTICLE-206025doi:10.1021/cr0501846View record in Web of Science URL: ://WOS:000249839900009 Record created on 2015-03-03, modified on 2017-05-12

Biocatalysis in ionic liquids

Abstract: Roger Sheldon (1942) received a PhD in organic chemistry from the University of Leicester (UK) in 1967. This was followed by post-doctoral studies with Prof. Jay Kochi in the U.S. From 1969 to 1980 he was with Shell Research in Amsterdam and from 1980 to 1990 he was R&D Director of DSM Andeno. In 1991 he moved to his present position as Professor of organic chemistry and catalysis at the Delft University of Technology (The Netherlands). His primary research interests are in the application of catalytic methodologies—homogeneous, heterogeneous and enzymatic—in organic synthesis, particularly in relation to fine chemicals production. He developed the concepts of E factors and atom utilization for assessing the environmental impact of chemical processes.

Highly efficient organic devices based on electrically doped transport layers.

Abstract: Most present-day semiconductor devices use inorganic crystalline materials, with single-crystalline silicon dominating other materials like GaAs by about a factor of 1000. Despite the advantages of single-crystalline inorganic semiconductors like high room-temperature mobility (up to 1000 cm2/(V s)) and high stability, these materials are less suitable for low-cost and large-area applications. Additionally, silicon is an indirect semiconductor and therefore is not well suited for optoelectronic applications like light-emitting diodes. Solar cells from silicon are expensive and require a large amount of energy for their fabrication, leading to a long energy payback time. As an alternative, organic semiconductors have recently gained much attention (for review articles, see refs 1 -3 (OLEDs), ref 4 (organic electronics in general), and refs 5 and 6 (organic solar cells)). Originally, much of the research concentrated on single crystals, which can have mobilities of a few cm2/(V s) at room temperature and even much higher values at low temperature, as shown in the pioneering work of Karl et al.7 However, for practical applications, thinfilm organic semiconductors with disordered morphology, such as evaporated small-molecule compounds or polymers processed from solution, are prevailing. Organic semiconductors are already broadly applied as photoconductors for copiers and laser printers. * Corresponding author. E-mail: leo@iapp.de. Web address: www.iapp.de. 1233 Chem. Rev. 2007, 107, 1233−1271