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Summary The High-Throughput Experimental Materials Database (HTEM-DB, htem.nrel.gov) is a repository of inorganic thin-film materials data collected during combinatorial experiments at the National Renewable Energy Laboratory (NREL). This data asset is enabled by NREL's Research Data Infrastructure (RDI), a set of custom data tools that collect, process, and store experimental data and metadata. Here, we describe the experimental data flow from the RDI to the HTEM-DB to illustrate the strategies and best practices currently used for materials data at NREL. Integration of the data tools with experimental instruments establishes a data communication pipeline between experimental researchers and data scientists. This work motivates the creation of similar workflows at other institutions to aggregate valuable data and increase their usefulness for future machine learning studies. In turn, such data-driven studies can greatly accelerate the pace of discovery and design in the materials science domain., Graphical abstract, Highlights • Automated curation of experimental materials data • Integration of data tools into the experimental laboratory • Simple, effective, and flexible data archival system • Collection of metadata for enhanced total data value, The bigger picture For machine learning to make significant contributions to a scientific domain, algorithms must ingest and learn from high-quality, large-volume datasets. The Research Data Infrastructure (RDI) that feeds the High-Throughput Experimental Materials Database (HTEM-DB, htem.nrel.gov) provides such a dataset from existing experimental data streams at the National Renewable Energy Laboratory (NREL). The described methods for curating experimental data can be applied to other materials research laboratory settings, paving the way for increased application of machine learning to materials science. In turn, the resulting new materials and new knowledge will benefit the society by advancing new technologies in energy, fuels, computing, security, and other important areas., This article describes the Research Data Infrastructure (RDI) and its application to create the High-Throughput Experimental Materials Database (HTEM-DB, htem.nrel.gov) at the National Renewable Energy Laboratory (NREL). RDI is a set of custom data tools that collect, process, and store experimental data and metadata, enabling the HTEM-DB repository for inorganic thin-film materials data collected during combinatorial experiments. This coupled experimental and data workflow from the RDI to the HTEM-DB illustrates the best practices currently used for materials data at NREL.

Ternary nitride semiconductors with wurtzite-derived crystal structures are an emerging class of materials for optoelectronic applications compatible with GaN and related III–V compounds. In particular, II–IV–V2 materials such as ZnSnN2 and ZnGeN2 have been very actively studied for applications in photovoltaics and light emitting devices. However, many other possible wurtzite-derived ternary nitrides have not been reported, and hence their optical and electrical properties remain unknown. Here, we report on Zn2SbN3 – the first Sb-based nitride and a photoactive semiconductor. Surprisingly, Zn2SbN3 contains Sb in the highest (5+) oxidation state, and in the unusual tetrahedral coordination. This new Zn2SbN3 material has a solar-matched 1.6–1.7 eV band gap and shows near-band-edge room-temperature photoluminescence, demonstrating its promise as an optoelectronic semiconductor. Finally, Zn2SbN3 can be synthesized at low temperature under a wide range of processing conditions, despite being metastable according to theoretical calculations. All these results, as well as the band position measurements, indicate that Zn2SbN3 is a promising emerging semiconductor for applications as an absorber in photovoltaic- and photoelectrochemical solar cells.

Mixed lead–tin hybrid perovskite alloy CH3NH3(Pb1–x Sn x )I3 attracted significant attention lately because of the reduction of its band gap below both end compounds, which makes it a promising bottom cell material in all-perovskite tandem solar cells. The effect is a consequence of a strongly nonlinear dependence of the alloy band gap on chemical composition. Here, we use electronic structure calculations at different levels of theory (density functional theory (DFT), hybrid DFT, and QSGW, with and without spin–orbit interactions) to investigate the presently elusive origin of this effect. Contrary to current conflicting studies, our results show that neither spin–orbit interactions nor the composition induced changes of the crystal structure and ordering of atoms contributes to the nonlinearity of the band gap. We find that the strong nonlinearity is primarily a consequence of chemical effects, i.e., the mismatch in energy between s and p atomic orbitals of Pb and Sn, which form the band edges of the al...

We report on design of optoelectronic properties in previously unreported metastable tin titanium nitride alloys with spinel crystal structure. Theoretical calculations predict that Ti alloying in metastable Sn3N4 compound should improve hole effective mass by up to 1 order of magnitude, while other optical bandgaps remains in the 1–2 eV range up to x ∼ 0.35 Ti composition. Experimental synthesis of these metastable alloys is predicted to be challenging due to high required nitrogen chemical potential (ΔμN ≥ +1.0 eV) but proven to be possible using combinatorial cosputtering from metal targets in the presence of nitrogen plasma. Characterization experiments confirm that thin films of such (Sn1–xTix)3N4 alloys can be synthesized up to x = 0.45 composition, with suitable optical band gaps (1.5–2.0 eV), moderate electron densities (1017 to 1018 cm–3), and improved photogenerated hole transport (by 5×). Overall, this study shows that it is possible to design the metastable nitride materials with properties su...

Solar energy has the potential to play a central role in the future global energy system because of the scale of the solar resource, its predictability, and its ubiquitous nature. Global installed solar photovoltaic (PV) capacity exceeded 500 GW at the end of 2018, and an estimated additional 500 GW of PV capacity is projected to be installed by 2022–2023, bringing us into the era of TW-scale PV. Given the speed of change in the PV industry, both in terms of continued dramatic cost decreases and manufacturing-scale increases, the growth toward TW-scale PV has caught many observers, including many of us (1), by surprise. Two years ago, we focused on the challenges of achieving 3 to 10 TW of PV by 2030. Here, we envision a future with ∼10 TW of PV by 2030 and 30 to 70 TW by 2050, providing a majority of global energy. PV would be not just a key contributor to electricity generation but also a central contributor to all segments of the global energy system. We discuss ramifications and challenges for complementary technologies (e.g., energy storage, power to gas/liquid fuels/chemicals, grid integration, and multiple sector electrification) and summarize what is needed in research in PV performance, reliability, manufacturing, and recycling.

Inorganic nitrides with wurtzite crystal structures are well-known semiconductors used in optical and electronic devices. In contrast, rocksalt-structured nitrides are known for their superconducting and refractory properties. Breaking this dichotomy, here we report ternary nitride semiconductors with rocksalt crystal structures, remarkable electronic properties, and the general chemical formula Mg x TM 1−x N ( TM = Ti, Zr, Hf, Nb). Our experiments show that these materials form over a broad metal composition range, and that Mg-rich compositions are nondegenerate semiconductors with visible-range optical absorption onsets (1.8 to 2.1 eV) and up to 100 cm 2 V −1 ⋅s −1 electron mobility for MgZrN 2 grown on MgO substrates. Complementary ab initio calculations reveal that these materials have disorder-tunable optical absorption, large dielectric constants, and electronic bandgaps that are relatively insensitive to disorder. These ternary Mg x TM 1−x N semiconductors are also structurally compatible both with binary TM N superconductors and main-group nitride semiconductors along certain crystallographic orientations. Overall, these results highlight Mg x TM 1−x N as a class of materials combining the semiconducting properties of main-group wurtzite nitrides and rocksalt structure of superconducting transition-metal nitrides.

Exploratory synthesis in new chemical spaces is the essence of solid-state chemistry. However, uncharted chemical spaces can be difficult to navigate, especially when materials synthesis is challenging. Nitrides represent one such space, where stringent synthesis constraints have limited the exploration of this important class of functional materials. Here, we employ a suite of computational materials discovery and informatics tools to construct a large stability map of the inorganic ternary metal nitrides. Our map clusters the ternary nitrides into chemical families with distinct stability and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation-from which we experimentally realized seven new Zn- and Mg-based ternary nitrides. By extracting the mixed metallicity, ionicity and covalency of solid-state bonding from the density functional theory (DFT)-computed electron density, we reveal the complex interplay between chemistry, composition and electronic structure in governing large-scale stability trends in ternary nitride materials.

The Solar Energy Research Institute for India and the United States (SERIIUS - http://www.seriius.org) is dedicated to creating a bi-national network of its 40 partners with members from academia, national laboratories, non-profit organizations, and industry to foster new ideas and collaborations to expedite a sustainable solar industry in the US and in India. SERIIUS is developing disruptive technologies through foundational research in sustainable photovoltaics (PV), multi-scale concentrating solar power (CSP) and coupled to an analysis activity to address the critical barriers for solar energy development in India that intersect the grand challenges for solar energy in the U.S. The consortium has published over 330 papers and conference proceedings of which 45 are joint between India and the US. SERIIUS has engaged overs 200 graduate students and had 30 binational intern exchanges.

Manganese oxide films are desirable oxygen evolution reaction (OER) catalysts due to their stability in acidic solutions and viability as earth-abundant materials. Enhanced catalytic activity of MnO2 incorporated with Mn3+ provides an imperative for understanding the structural and electronic effects giving rise to the superior OER catalysis. We show that (i) Mn3+ is stabilized kinetically in tetrahedral sites and (ii) its presence strains the oxide lattice, leading to a favorable disposition of oxide-based vs. metal-based energy levels that favors enhanced OER activity. The results herein offer a design concept of exploiting ion-induced lattice strain for creating superior metal oxide OER catalysts.

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn3+ We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn3+ may be introduced into MnO2 by an electrochemically induced comproportionation reaction with Mn2+ and that Mn3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn3+-activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies show that Mn3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn3+(Td) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the δ-MnO2 polymorph incorporating Mn3+ ions.

The Gibbs energy, G, determines the equilibrium conditions of chemical reactions and materials stability. Despite this fundamental and ubiquitous role, G has been tabulated for only a small fraction of known inorganic compounds, impeding a comprehensive perspective on the effects of temperature and composition on materials stability and synthesizability. Here, we use the SISSO (sure independence screening and sparsifying operator) approach to identify a simple and accurate descriptor to predict G for stoichiometric inorganic compounds with ~50 meV atom−1 (~1 kcal mol−1) resolution, and with minimal computational cost, for temperatures ranging from 300–1800 K. We then apply this descriptor to ~30,000 known materials curated from the Inorganic Crystal Structure Database (ICSD). Using the resulting predicted thermochemical data, we generate thousands of temperature-dependent phase diagrams to provide insights into the effects of temperature and composition on materials synthesizability and stability and to establish the temperature-dependent scale of metastability for inorganic compounds., Materials databases currently neglect the temperature effect on compound thermodynamics. Here the authors introduce a Gibbs energy descriptor enabling the high-throughput prediction of temperature-dependent thermodynamics across a wide range of compositions and temperatures for inorganic solids.

Mixing materials with different crystal structures leads to new phases that otherwise would require negative pressure to be made., The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material’s structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures—a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixing two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2× to 4× lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. This example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties—materials that are otherwise nearly impossible to make.

We report on the theoretical prediction and experimental realization of new ternary zinc molybdenum nitride compounds. We used theory to identify previously unknown ternary compounds in the Zn-Mo-N systems, Zn3MoN4 and ZnMoN2, and to analyze their bonding environment. Experiments show that Zn-Mo-N alloys can form in broad composition range from Zn3MoN4 to ZnMoN2 in the wurtzite-derived structure, accommodating very large off-stoichiometry. Interestingly, the measured wurtzite-derived structure of the alloys is metastable for the ZnMoN2 stoichiometry, in contrast to the Zn3MoN4 stoichiometry, where ordered wurtzite is predicted to be the ground state. The formation of Zn3MoN4-ZnMoN2 alloy with wurtzite-derived crystal structure is enabled by the concomitant ability of Mo to change oxidation state from +VI in Zn3MoN4 to +IV in ZnMoN2, and the capability of Zn to contribute to the bonding states of both compounds, an effect that we define as "redox-mediated stabilization". The stabilization of Mo in both the +VI and +IV oxidation states is due to the intermediate electronegativity of Zn, which enables significant polar covalent bonding in both Zn3MoN4 and ZnMoN2 compounds. The smooth change in the Mo oxidation state between Zn3MoN4 and ZnMoN2 stoichiometries leads to a continuous change in optoelectronic properties-from resistive and semitransparent Zn3MoN4 to conductive and absorptive ZnMoN2. The reported redox-mediated stabilization in zinc molybdenum nitrides suggests there might be many undiscovered ternary compounds with one metal having an intermediate electronegativity, enabling significant covalent bonding, and another metal capable of accommodating multiple oxidation states, enabling stoichiometric flexibility.

Exploratory synthesis in new chemical spaces is the essence of solid-state chemistry. However, uncharted chemical spaces can be difficult to navigate, especially when materials synthesis is challenging. Nitrides represent one such space, where stringent synthesis constraints have limited the exploration of this important class of functional materials. Here, we employ a suite of computational materials discovery and informatics tools to construct a large stability map of the inorganic ternary metal nitrides. Our map clusters the ternary nitrides into chemical families with distinct stability and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation-from which we experimentally realized seven new Zn- and Mg-based ternary nitrides. By extracting the mixed metallicity, ionicity and covalency of solid-state bonding from the density functional theory (DFT)-computed electron density, we reveal the complex interplay between chemistry, composition and electronic structure in governing large-scale stability trends in ternary nitride materials.

Theoretically predicted metastable phases are realized in thin-film synthesis of Mn1−xZnxO and Sn1−xCaxS alloys., Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the critical composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region.

As the world’s demand for energy grows, the search for cost competitive and earth abundant thin film photovoltaic absorbers is becoming increasingly important. A promising approach to tackle this challenge is through thin film photovoltaics made of elements that are abundant in the Earth’s crust. In this work, we focus on Cu2SnS3, a promising earth abundant absorber material. Recent publications have presented 3% and 6% device efficiencies using Cu2SnS3-based absorber materials and alloys, respectively. However, little is understood about the fundamental defect and doping physics of this material, which is needed for further improvements in device performance. Here, we identify the origins of the changes in doping in sputtered cubic Cu2SnS3 thin films using combinatorial experiments and first-principles theory. Experimentally, we find that the cubic Cu2SnS3 has a large phase width and that the electrical conductivity increases with increasing Cu and S content in the films, which cannot be fully explained ...

Recently, there has been an explosive growth in research based on hybrid lead–halide perovskites for photovoltaics owing to rapid improvements in efficiency. The advent of these materials for solar applications has led to widespread interest in understanding the key enabling properties of these materials. This has resulted in renewed interest in related compounds and a search for materials that may replicate the defect-tolerant properties and long lifetimes of the hybrid lead-halide perovskites. Given the rapid pace of development of the field, the rises in efficiencies of these systems have outpaced the more basic understanding of these materials. Measuring or calculating the basic properties, such as crystal/electronic structure and composition, can be challenging because some of these materials have anisotropic structures, and/or are composed of both heavy metal cations and volatile, mobile, light elements. Some consequences are beam damage during characterization, composition change under vacuum, or compound effects, such as the alteration of the electronic structure through the influence of the substrate. These effects make it challenging to understand the basic properties integral to optoelectronic operation. Compounding these difficulties is the rapid pace with which the field progresses. This has created an ongoing need to continually evaluate best practices with respect to characterization and calculations, as well as to identify inconsistencies in reported values to determine if those inconsistencies are rooted in characterization methodology or materials synthesis. This article describes the difficulties in characterizing hybrid lead–halide perovskites and new materials and how these challenges may be overcome. The topic was discussed at a seminar at the 2015 Materials Research Society Fall Meeting & Exhibit. This article highlights the lessons learned from the seminar and the insights of some of the attendees, with reference to both recent literature and controlled experiments to illustrate the challenges discussed. The focus in this article is on crystallography, composition measurements, photoemission spectroscopy, and calculations on perovskites and new, related absorbers. We suggest how the reporting of the important artifacts could be streamlined between groups to ensure reproducibility as the field progresses.

The annual potential of solar energy far exceeds the world's total energy consumption. However, the vision of photovoltaics (PVs) providing a substantial fraction of global electricity generation and total energy demand is far from being realized. What technical, infrastructure, economic, and policy barriers need to be overcome for PVs to grow to the multiple terawatt (TW) scale? We assess realistic future scenarios and make suggestions for a global agenda to move toward PVs at a multi-TW scale.

© 2016 Author(s). Recent advances in theoretical structure prediction methods and high-throughput computational techniques are revolutionizing experimental discovery of the thermodynamically stable inorganic materials. Metastable materials represent a new frontier for these studies, since even simple binary non-ground state compounds of common elements may be awaiting discovery. However, there are significant research challenges related to non-equilibrium thin film synthesis and crystal structure predictions, such as small strained crystals in the experimental samples and energy minimization based theoretical algorithms. Here, we report on experimental synthesis and characterization, as well as theoretical first-principles calculations of a previously unreported mixed-valent binary tin nitride. Thin film experiments indicate that this novel material is N-deficient SnN with tin in the mixed ii/iv valence state and a small low-symmetry unit cell. Theoretical calculations suggest that the most likely crystal structure has the space group 2 (SG2) related to the distorted delafossite (SG166), which is nearly 0.1 eV/atom above the ground state SnN polymorph. This observation is rationalized by the structural similarity of the SnN distorted delafossite to the chemically related Sn3N4spinel compound, which provides a fresh scientific insight into the reasons for growth of polymorphs of metastable materials. In addition to reporting on the discovery of the simple binary SnN compound, this paper illustrates a possible way of combining a wide range of advanced characterization techniques with the first-principle property calculation methods, to elucidate the most likely crystal structure of the previously unreported metastable materials.

Meeting our future global energy needs in an environmentally responsible way is perhaps the greatest challenge facing the world in the twenty first century. The discovery of new functional materials is critical to developing the needed disruptive technologies for energy conversion, delivery, storage, and use. Remarkable advances in theory and high-throughput materials synthesis and characterization are enabling a new approach to new materials discovery where theory can directly guide experimental materials discovery and development. This talk will present recent results from a number of research groups within the Next Generation for Materials by Design (CNGMD) Energy Frontier Research Center (EFRC), a multi-institution funded by DOE. Our overall goal is to design, discover and synthesize new energy-relevant functional materials, including non-equilibrium structures, with targeted functionalities by integrating theory, high-throughput computation, synthesis, and characterization. Our focus is on semiconductor materials for renewable energy and energy efficiency applications including solar energy conversion, solid-state lighting, solar fuel production and piezoelectrics. A primary goal is to incorporate functional metastable materials into materials by design and establish ranges for materials metastability as a function of the chemistry, energetics, and structure. We are examining three classes of metastable systems: defects, polymorphs, and solid solutions (alloys). We are also trying to develop a systematic theory-driven approach to guide the synthesis of new materials—including metastable systems—by coupling theory and state-of-the-art in-situ characterization to probe materials growth pathways. Highlights from our research will be presented including: Pnictide Search where we are exploring new metal nitrides to discover new functional semiconductor materials; Polymorphs and Synthesizability where we are understanding energy landscapes and identifying synthetic pathways for specific polymorphs focusing on Mn and Ti oxides; Chalcogenide Alloys where we predict and guide the synthesis of new functional semiconductor alloy materials; and Perovskite-Inspired Materials Search which designs new materials based on the electronic features of defect tolerance and long carrier lifetimes observed in hybrid organic-inorganic halide perovskites.

We have synthesized a series of CO2-soluble polymeric extractants with multiple ligand sites for CO2-based metal extractions. The CO2-soluble polymers were prepared via free-radical copolymerization of a fluorinated acrylate with a series of acrylate- or styrene-based monomers functionalized with ligand sites or ligand precursors. These polymers have high solubility in CO2; up to 30 wt % of a polymer with 15 mol % of a ligand-based monomer can be solubilized in liquid CO2 at 25 °C at 140 bar. Copper and europium extractions have been performed with β-diketone- and phosphonate-functionalized polymers, respectively. Preliminary extractions with copper nitrate were carried out at ligand-to-metal ratios of 1:1 and 2.7:1, resulting in 25−37% and 59% efficiency, respectively, suggesting a ligand binding stoichiometry of 2 for efficient extraction. Europium luminescence studies demonstrate that europium is bound to the polymer along with four water molecules in the inner coordination sphere.

Advanced oxidation technologies (AOTs), which involve the in situ generation of highly potent chemical oxidants, such as the hydroxyl radical (áOH), have emerged as an important class of technologies for accelerating the oxidation (and hence removal) of a wide range of organic contaminants in polluted water and air. In this report, standard figures-of-merit are proposed for the comparison and evaluation of these waste treatment technologies. These figures-of-merit are based on electric-energy consumption (for electric-energy-driven systems) or collector area (for solar-energy-driven systems). They fit within two phenomenological kinetic order regimes: 1) for high contaminant concentrations (electric energy per mass, E EM, or collector area per mass, A CM) and 2) for low concentrations (electric energy per order of magnitude, E EO, or collector area per order of magnitude, A CO). Furthermore, a simple understanding of the overall kinetic behavior of organic contaminant removal in a waste stream (i.e., whether zero- or first-order) is shown to be necessary for the description of meaningful electric- or solar-energy efficiencies. These standard figures-of-merit provide a direct link to the electric- or solar-energy efficiency (lower values mean higher efficiency) of an advanced oxidation technology, independent of the nature of the system, and therefore allow for direct comparison of widely disparate AOTs. These figures-of-merit are also shown to be inversely proportional to fundamental efficiency factors, such as the lamp efficiency (for electrical systems), the fraction of the emitted light that is absorbed in the aqueous solution, and the quantum yield of generation of active radicals.

Contents Green Chemistry in the International Context The Concept of green Chemistry Definition of green chemistry | Green chemistry: Why now? | The historical context of green chemistry | The emergence of green chemistry The Content of Green Chemistry Areas of green chemistry | Preliminary remarks | Alternative feedstocks | Benign reagents/synthetic pathways | Synthetic transformations | Solvents/reaction conditions Green Chemistry in the International Context It has come to be recognized in recent years, that the science of chemistry is central to addressing the problems facing the environment. Through the utilization of the various subdisciplines of chemistry and the molecular sciences, there is an increasing appreciation that the emerging area of green chemistry1is needed in the design and attainment of sustainable development. A central driving force in this increasing awareness is that green chemistry accomplishes both economic and environmental goals simultaneously through the use of sound, fundamental scientific principles. Recently, a basic strategy has been proposed for implementing the relationships between industry and academia, and hence, funding of the research that constitutes the engine of economic advancement; it is what many schools of economics call the "triple bottom line" philosophy, meaning that an enterprise will be economically sustainable if the objectives of environmental protection, societal benefit, and market advantage are all satisfied2. Triple bottom line is a strong idea for evaluating the success of environmental technologies. It is clear that the best environmentally friendly technology or discovery will not impact on the market if it is not economically advantageous; in the same way, the market that ignores environmental needs and human involvement will not prosper. This is the challenge for the future of the chemical industry, its development being strongly linked to the extent to which environmental and human needs can be reconciled with new ideas in fundamental research. On the other hand, it should be easy to foresee that the success of environmentally friendly reactions, products, and processes will improve competitiveness within the chemical industry. If companies are able to meet the needs of society, people will influence their own governments to foster those industries attempting such environmental initiatives. Of course, fundamental research will play a central role in achieving these worthy objectives. What we call green chemistry may in fact embody some of the most advanced perspectives and opportunities in chemical sciences. It is for these reasons that the International Union of Pure and Applied Chemistry (IUPAC) has a central role to play in advancing and promoting the continuing emergence and impact of green chemistry. When we think about how IUPAC furthers chemistry throughout the world, it is useful to refer to IUPAC's Strategic Plan. This plan demonstrates the direct relevance of the mission of IUPAC to green chemistry, and explains why there is growing enthusiasm for the pursuit of this new area as an appropriate activity of a scientific Union. The IUPAC Strategic Plan outlines among other goals: IUPAC will serve as a scientific, international, nongovernmental body in objectively addressing global issues involving the chemical sciences. Where appropriate, IUPAC will represent the interests of chemistry in governmental and nongovernmental forums. IUPAC will provide tools (e.g., standardized nomenclature and methods) and forums to help advance international research in the chemical sciences. IUPAC will assist chemistry-related industry in its contributions to sustainable development, wealth creation, and improvement in the quality of life. IUPAC will facilitate the development of effective channels of communication in the international chemistry community. IUPAC will promote the service of chemistry to society in both developed and developing countries. IUPAC will utilize its global perspective to contribute toward the enhancement of education in chemistry and to advance the public understanding of chemistry and the scientific method. IUPAC will make special efforts to encourage the career development of young chemists. IUPAC will broaden the geographical base of the Union and ensure that its human capital is drawn from all segments of the world chemistry community. IUPAC will encourage worldwide dissemination of information about the activities of the Union. IUPAC will assure sound management of its resources to provide maximum value for the funds invested in the Union. Through the vehicle of green chemistry, IUPAC can engage and is engaging the international community in issues of global importance to the environment and to industry, through education of young and established scientists, the provision of technical tools, governmental engagement, communication to the public and scientific communities, and the pursuit of sustainable development. By virtue of its status as a leading and internationally representative scientific body, IUPAC is able to collaborate closely in furthering individual national efforts as well as those of multinational entities. An important example of such collaboration in the area of green chemistry is that of IUPAC with the Organization for the Economical Cooperation and Development (OECD) in the project on "Sustainable Chemistry", aimed at promoting increased awareness of the subject in the member countries. During a meeting of the Environment Directorate (Paris, 6 June 1999), it was proposed that United States and Italy co-lead the activity, and that implementation of five recommendations to the member countries be accorded the highest priority, namely: research and development awards and recognition for work on sustainable chemistry exchange of technical information related to sustainable chemistry guidance on activities and tools to support sustainable chemistry programs sustainable chemistry education These recommendations were perceived to have socio-economic implications for worldwide implementation of sustainable chemistry. How IUPAC and, in particular, its Divisions can contribute to this effort is under discussion. IUPAC is recognized for its ability to act as the scientific counterpart to OECD for all recommendations and activities. Although the initiatives being developed by the OECD are aimed primarily at determining the role that national institutions can play in facilitating the implementation and impact of green chemistry, it is recognized that each of these initiatives also has an important scientific component. Whether it is developing criteria or providing technical assessment for awards and recognition, identifying appropriate scientific areas for educational incorporation, or providing scientific insight into the areas of need for fundamental research and development, IUPAC can play and is beginning to play an important role as an international scientific authority on green chemistry. Other multinational organizations including, among others, the United Nations, the European Union, and the Asian Pacific Economic Community, are now beginning to assess the role that they can play in promoting the implementation of green chemistry to meet environmental and economic goals simultaneously. As an alternative to the traditional regulatory framework often implemented as a unilateral strategy, multinational governmental organizations are discovering that green chemistry as a nonregulatory, science-based approach, provides opportunities for innovation and economic development that are compatible with sustainable development. In addition, individual nations have been extremely active in green chemistry and provide plentiful examples of the successful utilization of green chemistry technologies. There are rapidly growing activities in government, industry, and academia in the United States, Italy, the United Kingdom, the Netherlands, Spain, Germany, Japan, China, and many other countries in Europe and Asia, that testify to the importance of green chemistry to the future of the central science of chemistry around the world. Organizations and Commissions currently involved in programs in green chemistry at the national or international level include, for example: U.S. Environmental Protection Agency (EPA), with the "Green Chemistry Program" which involves, among others, the National Science Foundation, the American Chemical Society, and the Green Chemistry Institute; European Directorate for R&D (DG Research), which included the goals of sustainable chemistry in the actions and research of the European Fifth Framework Programme; Interuniversity Consortium "Chemistry for the Environment", which groups about 30 Italian universities interested in environmentally benign chemistry and funds their research groups; UK Royal Society of Chemistry, which promotes the concept of green chemistry through a "UK Green Chemistry Network" and the scientific journal Green Chemistry; UNIDO-ICS (International Centre for Science and High Technology of the United Nations Industrial Development Organization) which is developing a global program on sustainable chemistry focusing on catalysis and cleaner technologies with particular attention to developing and emerging countries (the program is also connected with UNIDO network of centers for cleaner production); and Monash University, which is the first organization in Australia to undertake a green chemistry program. Footnotes: 1. The terminology "green chemistry" or "sustainable chemistry" is the subject of debate. The expressions are intended to convey the same or very similar meanings, but each has its supporters and detractors, since "green" is vividly evocative but may assume an unintended political connotation, whereas "sustainable" can be paraphrased as "chemistry for a sustainable environment", and may be perceived as a less focused and less incisive description of the discipline. Other terms have been proposed, such as "chemistry for the environment" but this juxtaposition of keywords already embraces many diversified fields involving the environment, and does not capture the economic and social implications of sustainability. The Working Party decided to adopt the term green chemistry for the purpose of this overview. This decision does not imply official IUPAC endorsement for the choice. In fact, the IUPAC Committee on Chemistry and Industry (COCI) favors, and will continue to use sustainable chemistry to describe the discipline. 2. J. Elkington, < http://www.sustainability.co.uk/sustainability.htm

The selective epoxidation of olefinic alcohols with t-BuOOH in the presence of vanadium catalysts proceeds in liquid carbon dioxide with high conversions and selectivities. Rates measured in liquid CO2 for the oxovanadium(V) triisopropoxide catalyzed epoxidation of allylic and homoallylic alcohols using tert-butyl hydroperoxide are comparable to those measured in methylene chloride, toluene, and n-hexane. The reactivity of the vanadium(IV) bis(acetylacetonato) oxide catalyst in liquid CO2 was found to be substantially lower than in organic solvents, presumably due to its low solubility in CO2. Highly fluorinated acac-type ligands increased the catalytic reactivity of VO(acac)2-catalyzed epoxidations by enhancing catalyst precursor solubility. Heterogeneous epoxidation reactions were also carried out in liquid CO2 using vanadium complexes supported on cation-exchange polymers.

We report results from a study of the reactivity of the halogenated porphyrins tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPP)Cl] and β-octabromo-tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPPBr8)Cl] with dioxygen and cyclohexene in supercritical carbon dioxide. A lower limit for the solubility of the iron porphyrins in sc CO2 was determined. Both halogenated metalloporphyrins were active catalysts for oxidation of cyclohexene to epoxide and allylic oxidation products in sc CO2. In 12 h at 80°C, up to 350 and 580 turnovers were observed for Fe(TFPP)Cl and Fe(TFPPBr8)Cl, respectively. We have also explored several organic solvent reactions at high temperature and pressure to benchmark relative activity and selectivity. Activity is higher in organic solvent, but accompanied by substantial oxidation of, or reaction with the solvent. Selectivity for epoxidation with Fe(TFPPBr8)Cl is higher in sc CO2 than in organic solvents, with up to 34% cyclohexene oxide produced.

We demonstrate that asymmetric catalytic hydrogenation reactions can be conducted in supercritical CO{sub 2} and that, in some cases, higher enantioselectivities can be achieved in this solvent relative to conventional solvents. These preliminary studies effectively demonstrate the feasibility of conducting highly enantioselective hydrogenation reactions in supercritical CO{sub 2}. Importantly, we have shown that higher enantioselectivities may be achieved in supercritical CO{sub 2} relative to conventional solvents. 16 refs., 2 tabs.

The selective epoxidation of olefinic alcohols with t-BuOOH in the presence of vanadium catalysts proceeds in liquid carbon dioxide with high conversions and selectivities. Rates measured in liquid CO2 for the oxovanadium(V) triisopropoxide catalyzed epoxidation of allylic and homoallylic alcohols using tert-butyl hydroperoxide are comparable to those measured in methylene chloride, toluene, and n-hexane. The reactivity of the vanadium(IV) bis(acetylacetonato) oxide catalyst in liquid CO2 was found to be substantially lower than in organic solvents, presumably due to its low solubility in CO2. Highly fluorinated acac-type ligands increased the catalytic reactivity of VO(acac)2-catalyzed epoxidations by enhancing catalyst precursor solubility. Heterogeneous epoxidation reactions were also carried out in liquid CO2 using vanadium complexes supported on cation-exchange polymers.

Chemical manufacturing increasingly has to take environmental concerns into account, and chemical processes have to be designed accordingly. Baker and Tumas (page 1477) discuss recent developments in the area of homogeneous catalysis, where so-called biphasic catalysis is aiding separation of product and catalyst and facilitating catalyst recovery.

Benzimidazolines (dihydrobenzimidazoles) are shown for the first time to eliminate hydrogen (H2) by catalyzed reaction with protic compounds.

We report the activation of a 2,2'-bipyridine ligand within a class of (mono)cyclopentadienyl lanthanide complexes when reacted with carbon monoxide.

The goal of the "Opportunities for Catalysis Research in Carbon Management" workshop was to review within the context of greenhouse gas/carbon issues the current state of knowledge, barriers to further scientific and technological progress, and basic scientific research needs in the areas of H2 generation and utilization, light hydrocarbon activation and utilization, carbon dioxide activation, utilization, and sequestration, emerging techniques and research directions in relevant catalysis research, and in catalysis for more efficient transportation engines. Several overarching themes emerge from this review. First and foremost, there is a pressing need to better understand in detail the catalytic mechanisms involved in almost every process area mentioned above. This includes the structures, energetics, lifetimes, and reactivities of the species thought to be important in the key catalytic cycles. As much of this type of information as is possible to acquire would also greatly aid in better understanding perplexing, incomplete/inefficient catalytic cycles and in inventing new, efficient ones. The most productive way to attack such problems must include long-term, in-depth fundamental studies of both commercial and model processes, by conventional research techniques and, importantly, by applying various promising new physicochemical and computational approaches which would allow incisive, in situ elucidation of reaction pathways. There is also a consensus that more exploratory experiments, especially high-risk, unconventional catalytic and model studies, should be undertaken. Such an effort will likely require specialized equipment, instrumentation, and computational facilities. The most expeditious and cost-effective means to carry out this research would be by close coupling of academic, industrial, and national laboratory catalysis efforts worldwide. Completely new research approaches should be vigorously explored, ranging from novel compositions, fabrication techniques, reactors, and reaction conditions for heterogeneous catalysts, to novel ligands and ligation geometries (e.g., biomimetic), reaction media, and activation methods for homogeneous ones. The interplay between these two areas involving various hybrid and single-site supported catalyst systems should also be productive. Finally, new combinatorial and semicombinatorial means to rapidly create and screen catalyst systems are now available. As a complement to the approaches noted above, these techniques promise to greatly accelerate catalyst discovery, evaluation, and understanding. They should be incorporated in the vigorous international research effort needed in this field.

We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog.

Advanced oxidation processes (AOPs), which involve the in-situ generation of highly potent chemical oxidants such as the hydroxyl radical (•OH), have recently emerged as an important class of technologies for accelerating the oxidation and hence destruction of a wide range of organic contaminants in polluted water and air. We propose generally applicable standard figures-of-merit for comparing these waste treatment technologies. These figures-of-merit are based on electrical energy consumption within two phenomenological kinetic order regimes: one for high contaminant concentrations (electrical energy per mass, EE/M) and one for low concentrations (electrical energy per order of magnitude per m

We report the activation of a 2,2′-bipyridine ligand within a class of (mono)cyclopentadienyl lanthanide complexes when reacted with carbon monoxide.

A new phase-separable catalysis concept is demonstrated using supercritical carbon dioxide and the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate for hydrogenation of alkenes and carbon dioxide.

Non-covalent immobilization of [(R,R)-Me-(DuPHOS)Rh(COD)]OTf by interaction of the triflate counter ion with surface silanols of silica supports leads to an active, stable, enantioselective, asymmetric hydrogenation catalyst.

Catalysed alkene hydroboration proceeds in supercritical CO2 with several rhodium(I) complexes using tunable fluorinated ligands and shows higher regioselectivity relative to tetrahydrofuran or perfluoromethylcyclohexane.