Institute of Materials Research and Engineering

Electrocatalysis plays a central role in clean energy conversion, enabling a number of sustainable processes for future technologies. This review discusses design strategies for state-of-the-art heterogeneous electrocatalysts and associated materials for several different electrochemical transformations involving water, hydrogen, and oxygen, using theory as a means to rationalize catalyst performance. By examining the common principles that govern catalysis for different electrochemical reactions, we describe a systematic framework that clarifies trends in catalyzing these reactions, serving as a guide to new catalyst development while highlighting key gaps that need to be addressed. We conclude by extending this framework to emerging clean energy reactions such as hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, where the development of improved catalysts could allow for the sustainable production of a broad range of fuels and chemicals.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTSynthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent DevicesAndrew C. Grimsdale*†‡, Khai Leok Chan†§, Rainer E. Martin∥, Pawel G. Jokisz†, and Andrew B. Holmes*†View Author Information School of Chemistry, Bio21 Institute, University of Melbourne, 30 Flemington Road, Victoria 3010, Australia; School of Materials Science and Engineering, Nanyang Technological University, Nanyang Avenue, Republic of Singapore 639798; Institute of Materials Research and Engineering (IMRE) and the Agency for Science, Technology and Research (A*STAR), 3 Research Link, Singapore 117602; and F. Hoffmann-La Roche Ltd., Pharmaceuticals Division, Discovery Chemistry, CH-4070 Basel, Switzerland* Authors to whom correspondence should be addressed. E-mail: [email protected] and [email protected]†University of Melbourne. Telephone: +61 3 83442344. Fax: +61 3 83442384.‡Nanyang Technological University. Telephone: +65 67906728. Fax: +65 67909081.§Current address: Institute of Materials Research and Engineering.∥F. Hoffmann-La Roche Ltd.Cite this: Chem. Rev. 2009, 109, 3, 897–1091Publication Date (Web):February 19, 2009Publication History Received5 January 2007Published online19 February 2009Published inissue 11 March 2009https://pubs.acs.org/doi/10.1021/cr000013vhttps://doi.org/10.1021/cr000013vreview-articleACS PublicationsCopyright © 2009 American Chemical SocietyRequest reuse permissionsArticle Views36555Altmetric-Citations2418LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Conjugated polymers,Copolymers,Layers,Materials,Polymers Get e-Alerts

Due to their high energy density and low material cost, lithium-sulfur batteries represent a promising energy storage system for a multitude of emerging applications, ranging from stationary grid storage to mobile electric vehicles. This review aims to summarize major developments in the field of lithium-sulfur batteries, starting from an overview of their electrochemistry, technical challenges and potential solutions, along with some theoretical calculation results to advance our understanding of the material interactions involved. Next, we examine the most extensively-used design strategy: encapsulation of sulfur cathodes in carbon host materials. Other emerging host materials, such as polymeric and inorganic materials, are discussed as well. This is followed by a survey of novel battery configurations, including the use of lithium sulfide cathodes and lithium polysulfide catholytes, as well as recent burgeoning efforts in the modification of separators and protection of lithium metal anodes. Finally, we conclude with an outlook section to offer some insight on the future directions and prospects of lithium-sulfur batteries.

This comprehensive review provides a guide to design photothermal materials and systems for solar-driven water evaporation addressing the water–energy nexus.

Fluorescent bioprobes are powerful tools for analytical sensing and optical imaging, which allow direct visualization of biological analytes at the molecular level and offer useful insights into complex biological structures and processes. The sensing and imaging sensitivity of a bioprobe is determined by the brightness and contrast of its fluorescence before and after analyte binding. Emission from a fluorophore is often quenched at high concentration or in aggregate state, which is notoriously known as concentration quenching or aggregation-caused quenching (ACQ). The ACQ effect limits the label-to-analyte ratio and forces researchers to use very dilute solutions of fluorophores. It compels many probes to operate in a fluorescence "turn-off" mode with a narrow scope of practical applications. The unique aggregation-induced emission (AIE) process offers a straightforward solution to the ACQ problem. Typical AIE fluorogens are characterized by their propeller-shaped rotorlike structures, which undergo low-frequency torsional motions as isolated molecules and emit very weakly in solutions. Their aggregates show strong fluorescence mainly due to the restriction of their intramolecular rotations in the aggregate state. This fascinating attribute of AIE fluorogens provides a new platform for the development of fluorescence light-up molecules and photostable nanoaggregates for specific analyte detection and imaging. In this Account, we review our recent AIE work to highlight the utility of AIE effect in the development of new fluorescent bioprobes, which allows the use of highly concentrated fluorogens for biosensing and imaging. The simple design and fluorescence turn-on feature of the molecular AIE bioprobes offer direct visualization of specific analytes and biological processes in aqueous media with higher sensitivity and better accuracy than traditional fluorescence turn-off probes. The AIE dot-based bioprobes with different formulations and surface functionalities show advanced features over quantum dots and small molecule dyes, such as large absorptivity, high luminosity, excellent biocompatibility, free of random blinking, and strong photobleaching resistance. These features enable cancer cell detection, long term cell tracing, and tumor imaging in a noninvasive and high contrast manner. Recent research has significantly expanded the scope of biological applications of AIE fluorogens and offers new strategies to fluorescent bioprobe design. We anticipate that future development on AIE bioprobes will combine one- or multiphoton fluorescence with other modalities (e.g., magnetic resonance imaging) or functionalities (e.g. therapy) to fully demonstrate their potential as a new generation of theranostic reagent. In parallel, the advances in molecular biology will provide more specific bioreceptors, which will enable the development of next generation AIE bioprobes with high selectivity and sensitivity for molecular sensing and imaging.

Photovoltaic (PV) technologies for solar energy conversion represent promising routes to green and renewable energy generation. Despite relevant PV technologies being available for more than half a century, the production of solar energy remains costly, largely owing to low power conversion efficiencies of solar cells. The main difficulty in improving the efficiency of PV energy conversion lies in the spectral mismatch between the energy distribution of photons in the incident solar spectrum and the bandgap of a semiconductor material. In recent years, luminescent materials, which are capable of converting a broad spectrum of light into photons of a particular wavelength, have been synthesized and used to minimize the losses in the solar-cell-based energy conversion process. In this review, we will survey recent progress in the development of spectral converters, with a particular emphasis on lanthanide-based upconversion, quantum-cutting and down-shifting materials, for PV applications. In addition, we will also present technical challenges that arise in developing cost-effective high-performance solar cells based on these luminescent materials.

The hydrogen evolution reaction (HER) is an important energy conversion process that underpins many clean energy technologies including water splitting. Herein, we report for the first time the application of two-dimensional (2D) layered transition metal carbides, MXenes, as electrocatalysts for the HER. Our computational screening study of 2D layered M2XTx (M = metal; X = (C, N); and Tx = surface functional groups) predicts Mo2CTx to be an active catalyst candidate for the HER. We synthesized both Mo2CTx and Ti2CTx MXenes, and in agreement with our theoretical predictions, Mo2CTx was found to exhibit far higher HER activity than Ti2CTx. Theory suggests that the basal planes of Mo2CTx are catalytically active toward the HER, unlike in the case of widely studied MoS2, in which only the edge sites of the 2H phase are active. This work paves the way for the development of novel 2D layered materials that can be applied in a multitude of other clean energy reactions for a sustainable energy future.

Anti-reflective coatings (ARCs) have evolved into highly effective reflectance and glare reducing components for various optical and opto-electrical equipments. Extensive research in optical and biological reflectance minimization as well as the emergence of nanotechnology over the years has contributed to the enhancement of ARCs in a major way. In this study the prime objective is to give a comprehensive idea of the ARCs right from their inception, as they were originally conceptualized by the pioneers and lay down the basic concepts and strategies adopted to minimize reflectance. The different types of ARCs are also described in greater detail and the state-of-the-art fabrication techniques have been fully illustrated. The inspiration that ARCs derive from nature (‘biomimetics’) has been an area of major research and is discussed at length. The various materials that have been reportedly used in fabricating the ARCs have also been brought into sharp focus. An account of application of ARCs on solar cells and modules, contemporary research and associated challenges are presented in the end to facilitate a universal understanding of the ARCs and encourage future research.

The oxygen reduction reaction (ORR) is an important electrode reaction for energy storage and conversion devices based on oxygen electrocatalysis. This paper introduces the thermodynamics, reaction kinetics, reaction mechanisms, and reaction pathways of ORR in aqueous alkaline media. Recent advances of the catalysts for ORR were extensively reviewed, including precious metals, nonmetal-doped carbon, carbon–transition metal hybrids, transition metal oxides with spinel and perovskite structures, and so forth. The applications of those ORR catalysts to zinc–air batteries and alkaline fuel cells were briefly introduced. A concluding remark summarizes the current status of the reaction pathways, advanced catalysts, and the future challenges of the research and development of ORR.

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical to renewable energy conversion and storage technologies. Heteroatom-doped carbon nanomaterials have been reported to be efficient metal-free electrocatalysts for ORR in fuel cells for energy conversion, as well as ORR and OER in metal-air batteries for energy storage. We reported that metal-free three-dimensional (3D) graphene nanoribbon networks (N-GRW) doped with nitrogen exhibited superb bifunctional electrocatalytic activities for both ORR and OER, with an excellent stability in alkaline electrolytes (for example, KOH). For the first time, it was experimentally demonstrated that the electron-donating quaternary N sites were responsible for ORR, whereas the electron-withdrawing pyridinic N moieties in N-GRW served as active sites for OER. The unique 3D nanoarchitecture provided a high density of the ORR and OER active sites and facilitated the electrolyte and electron transports. As a result, the as-prepared N-GRW holds great potential as a low-cost, highly efficient air cathode in rechargeable metal-air batteries. Rechargeable zinc-air batteries with the N-GRW air electrode in a two-electrode configuration exhibited an open-circuit voltage of 1.46 V, a specific capacity of 873 mAh g(-1), and a peak power density of 65 mW cm(-2), which could be continuously charged and discharged with an excellent cycling stability. Our work should open up new avenues for the development of various carbon-based metal-free bifunctional electrocatalysts of practical significance.

The phosphorization of molybdenum leads to a good non-noble metal catalyst for the hydrogen evolution reaction in both acidic and alkaline conditions.

Significance A series of metal sulfides were systematically investigated as polar hosts to reveal the key parameters correlated to the energy barriers and polysulfide adsorption capability in Li−S batteries. The investigation demonstrates that the catalyzing oxidation capability of metal sulfides is critical in reducing the energy barrier and contributing to the remarkably improved battery performance. Density functional theory simulation allows us to identify the mechanism for how binding energy and polysulfides trapping dominate the Li 2 S decomposition process and overall battery performance. The understanding can serve as a general guiding principle for the rational design and screening of advanced materials for high-energy Li−S batteries.

Humans rely increasingly on sensors to address grand challenges and to improve quality of life in the era of digitalization and big data. For ubiquitous sensing, flexible sensors are developed to overcome the limitations of conventional rigid counterparts. Despite rapid advancement in bench-side research over the last decade, the market adoption of flexible sensors remains limited. To ease and to expedite their deployment, here, we identify bottlenecks hindering the maturation of flexible sensors and propose promising solutions. We first analyze challenges in achieving satisfactory sensing performance for real-world applications and then summarize issues in compatible sensor-biology interfaces, followed by brief discussions on powering and connecting sensor networks. Issues en route to commercialization and for sustainable growth of the sector are also analyzed, highlighting environmental concerns and emphasizing nontechnical issues such as business, regulatory, and ethical considerations. Additionally, we look at future intelligent flexible sensors. In proposing a comprehensive roadmap, we hope to steer research efforts towards common goals and to guide coordinated development strategies from disparate communities. Through such collaborative efforts, scientific breakthroughs can be made sooner and capitalized for the betterment of humanity.

The recent developments of lignin were reviewed in terms of different approaches to synthesize lignin-based copolymers, the resulting features and the potential applications of such copolymers.

Lead free perovskite solar cells based on a CsSnI3 light absorber with a spectral response from 950 nm is demonstrated. The high photocurrents noted in the system are a consequence of SnF2 addition which reduces defect concentrations and hence the background charge carrier density.

The design and characterization of metal-organic complexes for optoelectronic applications is an active area of research. The metal-organic complex offers unique optical and electronic properties arising from the interplay between the inorganic metal and the organic ligand. The ability to modify chemical structure through control over metal-ligand interaction on a molecular level could directly impact the properties of the complex. When deposited in thin film form, this class of materials enable the fabrication of a wide variety of low-cost electronic and optoelectronic devices. These include light emitting diodes, solar cells, photodetectors, field-effect transistors as well as chemical and biological sensors. Here we present an overview of recent development in metal-organic complexes with controlled molecular structures and tunable properties. Advances in extending the control of molecular structures to solid materials for energy conversion and information technology applications will be highlighted.

We demonstrate strong potential of computational screening and germanium iodide perovskite compounds for photovoltaic applications.

Optogenetics has revolutionized the experimental interrogation of neural circuits and holds promise for the treatment of neurological disorders. It is limited, however, because visible light cannot penetrate deep inside brain tissue. Upconversion nanoparticles (UCNPs) absorb tissue-penetrating near-infrared (NIR) light and emit wavelength-specific visible light. Here, we demonstrate that molecularly tailored UCNPs can serve as optogenetic actuators of transcranial NIR light to stimulate deep brain neurons. Transcranial NIR UCNP-mediated optogenetics evoked dopamine release from genetically tagged neurons in the ventral tegmental area, induced brain oscillations through activation of inhibitory neurons in the medial septum, silenced seizure by inhibition of hippocampal excitatory cells, and triggered memory recall. UCNP technology will enable less-invasive optical neuronal activity manipulation with the potential for remote therapy.

Solution-processed small-molecule p-DTS(FBTTh2)2:PC71BM bulk heterojunction (BHJ) solar cells with power conversion efficiency of 8.01% are demonstrated. The fill factor (FF) is sensitive to the thickness of a calcium layer between the BHJ layer and the Al cathode; for 20 nm Ca thickness, the FF is 73%, the highest value reported for an organic solar cell. The maximum external quantum efficiency exceeds 80%. After correcting for the total absorption in the cell through normal incidence reflectance measurements, the internal quantum efficiency approaches 100% in the spectral range of 600-650 nm and well over 80% across the entire spectral range from 400 to 700 nm. Analysis of the current-voltage (J-V) characteristics at various light intensities provides information on the different recombination mechanisms in the BHJ solar cells with different thicknesses of the Ca layer. Our analysis reveals that the J-V curves are dominated by first-order recombination from the short-circuit condition to the maximum power point and evolve to bimolecular recombination in the range of voltage from the maximum power point to the open-circuit condition in the optimized device with a Ca thickness of 20 nm. In addition, the normalized photocurrent density curves reveal that the charge collection probability remains high; about 90% of charges are collected even at the maximum power point. The dominance of bimolecular recombination only when approaching open circuit, the lack of Shockley-Read-Hall recombination at open circuit, and the high charge collection probability (97.6% at the short circuit and constant over wide range of applied voltage) lead to the high fill factor.

Abstract A composite made from the assembly of graphene oxide (GO) and copper‐centered metal organic framework (MOF) shows good performance as a tri‐functional catalyst in three important electrocatalysis reactions, namely: the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). One of the challenges in the area of electrocatalysis is to find an effective catalyst that will reduce, as well as generate, oxygen at moderate temperatures. The enhanced electrocatalytic properties and stability in acid of the GO‐MOF composite is due to the unqiue porous scaffold structure, improved charge transport and synergistic interactions between the GO and MOF. In polymer electrolyte membrane fuel cell testing, the GO‐incorporated Cu‐MOF composite delivers a power density that is 76% that of the commercial Pt catalyst.