Institute of Chemistry

Aggregation greatly boosts emission efficiency of the silole, turning it from a weak luminophor into a strong emitter.

Abstract Super‐hydrophobic surfaces, with a water contact angle (CA) greater than 150°, have attracted much interest for both fundamental research and practical applications. Recent studies on lotus and rice leaves reveal that a super‐hydrophobic surface with both a large CA and small sliding angle (α) needs the cooperation of micro‐ and nanostructures, and the arrangement of the microstructures on this surface can influence the way a water droplet tends to move. These results from the natural world provide a guide for constructing artificial super‐hydrophobic surfaces and designing surfaces with controllable wettability. Accordingly, super‐hydrophobic surfaces of polymer nanofibers and differently patterned aligned carbon nanotube (ACNT) films have been fabricated.

A novel non-fullerene electron acceptor (ITIC) that overcomes some of the shortcomings of fullerene acceptors, for example, weak absorption in the visible spectral region and limited energy-level variability, is designed and synthesized. Fullerene-free polymer solar cells (PSCs) based on the ITIC acceptor are demonstrated to exhibit power conversion efficiencies of up to 6.8%, a record for fullerene-free PSCs. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTSemiconducting π-Conjugated Systems in Field-Effect Transistors: A Material Odyssey of Organic ElectronicsChengliang Wang, Huanli Dong, Wenping Hu*, Yunqi Liu, and Daoben ZhuView Author Information Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China*Address: Zhongguancun North First No 2, Beijing, 100190, China. E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 4, 2208–2267Publication Date (Web):November 23, 2011Publication History Received15 November 2010Published online23 November 2011Published inissue 11 April 2012https://pubs.acs.org/doi/10.1021/cr100380zhttps://doi.org/10.1021/cr100380zreview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views44410Altmetric-Citations3145LEARN 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:Aromatic compounds,Hydrocarbons,Mobility,Reaction products,Thin films Get e-Alerts

Bulk heterojunction (BHJ) polymer solar cells (PSCs) sandwich a blend layer of conjugated polymer donor and fullerene derivative acceptor between a transparent ITO positive electrode and a low work function metal negative electrode. In comparison with traditional inorganic semiconductor solar cells, PSCs offer a simpler device structure, easier fabrication, lower cost, and lighter weight, and these structures can be fabricated into flexible devices. But currently the power conversion efficiency (PCE) of the PSCs is not sufficient for future commercialization. The polymer donors and fullerene derivative acceptors are the key photovoltaic materials that will need to be optimized for high-performance PSCs. In this Account, I discuss the basic requirements and scientific issues in the molecular design of high efficiency photovoltaic molecules. I also summarize recent progress in electronic energy level engineering and absorption spectral broadening of the donor and acceptor photovoltaic materials by my research group and others. For high-efficiency conjugated polymer donors, key requirements are a narrower energy bandgap (E(g)) and broad absorption, relatively lower-lying HOMO (the highest occupied molecular orbital) level, and higher hole mobility. There are three strategies to meet these requirements: D-A copolymerization for narrower E(g) and lower-lying HOMO, substitution with electron-withdrawing groups for lower-lying HOMO, and two-dimensional conjugation for broad absorption and higher hole mobility. Moreover, better main chain planarity and less side chain steric hindrance could strengthen π-π stacking and increase hole mobility. Furthermore, the molecular weight of the polymers also influences their photovoltaic performance. To produce high efficiency photovoltaic polymers, researchers should attempt to increase molecular weight while maintaining solubility. High-efficiency D-A copolymers have been obtained by using benzodithiophene (BDT), dithienosilole (DTS), or indacenodithiophene (IDT) donor unit and benzothiadiazole (BT), thienopyrrole-dione (TPD), or thiazolothiazole (TTz) acceptor units. The BDT unit with two thienyl conjugated side chains is a highly promising unit in constructing high-efficiency copolymer donor materials. The electron-withdrawing groups of ester, ketone, fluorine, or sulfonyl can effectively tune the HOMO energy levels downward. To improve the performance of fullerene derivative acceptors, researchers will need to strengthen absorption in the visible spectrum, upshift the LUMO (the lowest unoccupied molecular orbital) energy level, and increase the electron mobility. [6,6]-Phenyl-C(71)-butyric acid methyl ester (PC(70)BM) is superior to [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) because C(70) absorbs visible light more efficiently. Indene-C(60) bisadduct (ICBA) and Indene-C(70) bisadduct (IC(70)BA) show 0.17 and 0.19 eV higher LUMO energy levels, respectively, than PCBM, due to the electron-rich character of indene and the effect of bisadduct. ICBA and IC(70)BA are excellent acceptors for the P3HT-based PSCs.

The production of clean and renewable hydrogen through water splitting using photocatalysts has received much attention due to the increasing global energy crises. In this study, a high efficiency of the photocatalytic H(2) production was achieved using graphene nanosheets decorated with CdS clusters as visible-light-driven photocatalysts. The materials were prepared by a solvothermal method in which graphene oxide (GO) served as the support and cadmium acetate (Cd(Ac)(2)) as the CdS precursor. These nanosized composites reach a high H(2)-production rate of 1.12 mmol h(-1) (about 4.87 times higher than that of pure CdS nanoparticles) at graphene content of 1.0 wt % and Pt 0.5 wt % under visible-light irradiation and an apparent quantum efficiency (QE) of 22.5% at wavelength of 420 nm. This high photocatalytic H(2)-production activity is attributed predominantly to the presence of graphene, which serves as an electron collector and transporter to efficiently lengthen the lifetime of the photogenerated charge carriers from CdS nanoparticles. This work highlights the potential application of graphene-based materials in the field of energy conversion.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTSupramolecular Chirality in Self-Assembled SystemsMinghua Liu*, Li Zhang, and Tianyu WangView Author Information Beijing National Laboratory for Molecular Science (BNLMS), CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China*Phone: +86 10 82615803. E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 15, 7304–7397Publication Date (Web):July 20, 2015Publication History Received8 December 2014Published online20 July 2015Published inissue 12 August 2015https://pubs.acs.org/doi/10.1021/cr500671phttps://doi.org/10.1021/cr500671preview-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views53168Altmetric-Citations1612LEARN 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:Chirality,Molecular structure,Self organization,Supramolecular chemistry,Supramolecular structures and assemblies Get e-Alerts

Biomimetic research indicates that many phenomena regarding wettability in nature, such as the self-cleaning effect on a lotus leaf and cicada wing, the anisotropic dewetting behavior on a rice leaf, and striking superhydrophobic force provided by a water strider's leg, are all related to the unique micro- and nanostructures on the surfaces. It gives us much inspiration to realize special wettability on functional surfaces through the cooperation between the chemical composition and the surface micro- and nanostructures, which may bring great advantages in a wide variety of applications in daily life, industry, and agriculture. This Account reviews recent progress in these aspects.

Abstract Recent achievements in the construction of surfaces with special wettabilities, such as superhydrophobicity, superhydrophilicity, superoleophobicity, superoleophilicity, superamphiphilicity, superamphiphobicity, superhydrophobicity/superoleophilicity, and reversible switching between superhydrophobicity and superhydrophilicity, are presented. Particular attention is paid to superhydrophobic surfaces created via various methods and surfaces with reversible superhydrophobicity and superhydrophilicity that are driven by various kinds of external stimuli. The control of the surface micro‐/nanostructure and the chemical composition is critical for these special properties. These surfaces with controllable wettability are of great importance for both fundamental research and practical applications.

A nonfullerene-based polymer solar cell (PSC) that significantly outperforms fullerene-based PSCs with respect to the power-conversion efficiency is demonstrated for the first time. An efficiency of >11%, which is among the top values in the PSC field, and excellent thermal stability is obtained using PBDB-T and ITIC as donor and acceptor, respectively. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Understanding the origin of high activity of Fe-N-C electrocatalysts in oxygen reduction reaction (ORR) is critical but still challenging for developing efficient sustainable nonprecious metal catalysts in fuel cells and metal-air batteries. Herein, we developed a new highly active Fe-N-C ORR catalyst containing Fe-N(x) coordination sites and Fe/Fe3C nanocrystals (Fe@C-FeNC), and revealed the origin of its activity by intensively investigating the composition and the structure of the catalyst and their correlations with the electrochemical performance. The detailed analyses unambiguously confirmed the coexistence of Fe/Fe3C nanocrystals and Fe-N(x) in the best catalyst. A series of designed experiments disclosed that (1) N-doped carbon substrate, Fe/Fe3C nanocrystals or Fe-N(x) themselves did not deliver the high activity; (2) the catalysts with both Fe/Fe3C nanocrystals and Fe-N(x) exhibited the high activity; (3) the higher content of Fe-N(x) gave the higher activity; (4) the removal of Fe/Fe3C nanocrystals severely degraded the activity; (5) the blocking of Fe-N(x) downgraded the activity and the recovery of the blocked Fe-N(x) recovered the activity. These facts supported that the high ORR activity of the Fe@C-FeNC electrocatalysts should be ascribed to that Fe/Fe3C nanocrystals boost the activity of Fe-N(x). The coexistence of high content of Fe-N(x) and sufficient metallic iron nanoparticles is essential for the high ORR activity. DFT calculation corroborated this conclusion by indicating that the interaction between metallic iron and Fe-N4 coordination structure favored the adsorption of oxygen molecule. These new findings open an avenue for the rational design and bottom-up synthesis of low-cost highly active ORR electrocatalysts.

Organic electron-transporting materials are essential for the fabrication of organic p-n junctions, photovoltaic cells, n-channel field-effect transistors, and complementary logic circuits. Rylene diimides are a robust, versatile class of polycyclic aromatic electron-transport materials with excellent thermal and oxidative stability, high electron affinities, and, in many cases, high electron mobilities; they are, therefore, promising candidates for a variety of organic electronics applications. In this review, recent developments in the area of high-electron-mobility diimides based on rylenes and related aromatic cores, particularly perylene- and naphthalene-diimide-based small molecules and polymers, for application in high-performance organic field-effect transistors and photovoltaic cells are summarized and analyzed.

Organic photovoltaic cells (OPVs) are a promising cost-effective alternative to silicon-based solar cells, and possess light-weight, low-cost, and flexibility advantages. Significant progress has been achieved in the development of novel photovoltaic materials and device structures in the last decade. Nowadays small molecular semiconductors for OPVs have attracted considerable attention, due to their advantages over their polymer counterparts, including well-defined molecular structure, definite molecular weight, and high purity without batch to batch variations. The highest power conversion efficiencies of OPVs based on small molecular donor/fullerene acceptors or polymeric donor/fullerene acceptors are up to 6.7% and 8.3%, respectively, and meanwhile nonfullerene acceptors have also exhibited some promising results. In this review we summarize the developments in small molecular donors, acceptors (fullerene derivatives and nonfullerene molecules), and donor-acceptor dyad systems for high-performance multilayer, bulk heterojunction, and single-component OPVs. We focus on correlations of molecular chemical structures with properties, such as absorption, energy levels, charge mobilities, and photovoltaic performances. This structure-property relationship analysis may guide rational structural design and evaluation of photovoltaic materials (253 references).

Graphitic carbon nitride (g-C3N4) was produced on a large scale by the pyrolysis of urea under ambient pressure without additive assistance. The retainable pyrolysis-generated self-supporting atmosphere and the reaction temperature are two necessary conditions. This g-C3N4 as photocatalyst shows recyclable adsorption and photocatalytic activity under visible light.

Python‐based simulations of chemistry framework (P y SCF) is a general‐purpose electronic structure platform designed from the ground up to emphasize code simplicity, so as to facilitate new method development and enable flexible computational workflows. The package provides a wide range of tools to support simulations of finite‐size systems, extended systems with periodic boundary conditions, low‐dimensional periodic systems, and custom Hamiltonians, using mean‐field and post‐mean‐field methods with standard Gaussian basis functions. To ensure ease of extensibility, P y SCF uses the Python language to implement almost all of its features, while computationally critical paths are implemented with heavily optimized C routines. Using this combined Python/C implementation, the package is as efficient as the best existing C or Fortran‐based quantum chemistry programs. In this paper, we document the capabilities and design philosophy of the current version of the P y SCF package. WIREs Comput Mol Sci 2018, 8:e1340. doi: 10.1002/wcms.1340 This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Ab Initio Electronic Structure Methods Software > Quantum Chemistry

Recently, a lot of effort has been focused on improving the performance and exploring the electric properties of graphene. This article presents a summary of chemical doping of graphene aimed at tuning the electronic properties of graphene. p-Type and n-type doping of graphene achieved through surface transfer doping or substitutional doping and their applications based on doping are reviewed. Chemical doping for band gap tuning in graphene is also presented. It will be beneficial to designing high performance electronic devices based on chemically doped graphene.

An ethylene-glycol-mediated self-assembly process is adopted to synthesize 3D flowerlike nanostructures of iron oxide (see figure) using inexpensive and nontoxic ferric chloride. A two-stage growth process is identified during the morphological evolution of the iron oxide precursor. α-Fe2O3, γ-Fe2O3, and Fe3O4 with the same flowerlike structure are readily obtained from the same precursor but by different calcination procedures. The as-obtained iron oxides show excellent ability to remove various pollutants from water.

Significance Exceedingly high levels of fine particulate matter (PM) occur frequently in China, but the mechanism of severe haze formation remains unclear. From atmospheric measurements in two Chinese megacities and laboratory experiments, we show that the oxidation of SO 2 by NO 2 occurs efficiently in aqueous media under two polluted conditions: first, during the formation of the 1952 London Fog via in-cloud oxidation; and second, on fine PM with NH 3 neutralization during severe haze in China. We suggest that effective haze mitigation is achievable by intervening in the sulfate formation process with NH 3 and NO 2 emission control measures. Hence, our results explain the outstanding sulfur problem during the historic London Fog formation and elucidate the chemical mechanism of severe haze in China.

The future development of chemistry entails environmentally friendly and energy sustainable alternatives for organic transformations. Visible light photocatalysis can address these challenges, as reflected by recent intensive scientific endeavours to this end. This review covers state-of-the-art accomplishments in visible-light-induced selective organic transformations by heterogeneous photocatalysis. The discussion comprises three sections based on the photocatalyst type: metal oxides such as TiO2, Nb2O5 and ZnO; plasmonic photocatalysts like nanostructured Au, Ag or Cu supported on metal oxides; and polymeric graphitic carbon nitride. Finally, recent strides in bridging the gap between photocatalysis and other areas of catalysis will be highlighted with the aim of overcoming the existing limitations of photocatalysis by developing more creative synthetic methodologies.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTHelicenes: Synthesis and ApplicationsYun Shen†‡ and Chuan-Feng Chen†*View Author Information† Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China‡ Graduate School, Chinese Academy of Sciences, Beijing 100049, China*E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 3, 1463–1535Publication Date (Web):October 24, 2011Publication History Received25 March 2011Published online24 October 2011Published inissue 14 March 2012https://pubs.acs.org/doi/10.1021/cr200087rhttps://doi.org/10.1021/cr200087rreview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views34216Altmetric-Citations1179LEARN 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:Aromatic compounds,Chemical structure,Cyclization,Precursors,Substituents Get e-Alerts