Beijing University of Chemical Technology

Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5) Plot density-of-states and spectrum. (6) Topology analysis for electron density. Some other useful utilities involved in quantum chemistry studies are also provided. The built-in graph module enables the results of wavefunction analysis to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com.

In this study, the mechanical properties of epoxy nanocomposites with graphene platelets, single-walled carbon nanotubes, and multi-walled carbon nanotube additives were compared at a nanofiller weight fraction of 0.1 +/- 0.002%. The mechanical properties measured were the Young's modulus, ultimate tensile strength, fracture toughness, fracture energy, and the material's resistance to fatigue crack propagation. The results indicate that graphene platelets significantly out-perform carbon nanotube additives. The Young's modulus of the graphene nanocomposite was approximately 31% greater than the pristine epoxy as compared to approximately 3% increase for single-walled carbon nanotubes. The tensile strength of the baseline epoxy was enhanced by approximately 40% with graphene platelets compared to approximately 14% improvement for multi-walled carbon nanotubes. The mode I fracture toughness of the nanocomposite with graphene platelets showed approximately 53% increase over the epoxy compared to approximately 20% improvement for multi-walled carbon nanotubes. The fatigue resistance results also showed significantly different trends. While the fatigue suppression response of nanotube/epoxy composites degrades dramatically as the stress intensity factor amplitude is increased, the reverse effect is seen for graphene-based nanocomposites. The superiority of graphene platelets over carbon nanotubes in terms of mechanical properties enhancement may be related to their high specific surface area, enhanced nanofiller-matrix adhesion/interlocking arising from their wrinkled (rough) surface, as well as the two-dimensional (planar) geometry of graphene platelets.

Although biomedical applications of carbon nanotubes have been intensively studied in recent years, its sister, graphene, has been rarely explored in biomedicine. In this work, for the first time we study the in vivo behaviors of nanographene sheets (NGS) with polyethylene glycol (PEG) coating by a fluorescent labeling method. In vivo fluorescence imaging reveals surprisingly high tumor uptake of NGS in several xenograft tumor mouse models. Distinctive from PEGylated carbon nanotubes, PEGylated NGS shows several interesting in vivo behaviors including highly efficient tumor passive targeting and relatively low retention in reticuloendothelial systems. We then utilize the strong optical absorbance of NGS in the near-infrared (NIR) region for in vivo photothermal therapy, achieving ultraefficient tumor ablation after intravenous administration of NGS and low-power NIR laser irradiation on the tumor. Furthermore, no obvious side effect of PEGylated NGS is noted for the injected mice by histology, blood chemistry, and complete blood panel analysis in our pilot toxicity study. Although a lot more efforts are required to further understand the in vivo behaviors and the long-term toxicology of this new type of nanomaterials, our work is the first success of using carbon nanomaterials for efficient in vivo photothermal therapy by intravenous administration and suggests the great promise of graphene in biomedical applications, such as cancer treatment.

A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials.

Abstract Hierarchical flowerlike nickel hydroxide decorated on graphene sheets has been prepared by a facile and cost‐effective microwave‐assisted method. In order to achieve high energy and power densities, a high‐voltage asymmetric supercapacitor is successfully fabricated using Ni(OH) 2 /graphene and porous graphene as the positive and negative electrodes, respectively. Because of their unique structure, both of these materials exhibit excellent electrochemical performances. The optimized asymmetric supercapacitor could be cycled reversibly in the high‐voltage region of 0–1.6 V and displays intriguing performances with a maximum specific capacitance of 218.4 F g −1 and high energy density of 77.8 Wh kg −1 . Furthermore, the Ni(OH) 2 /graphene//porous graphene supercapacitor device exhibits an excellent long cycle life along with 94.3% specific capacitance retained after 3000 cycles. These fascinating performances can be attributed to the high capacitance and the positive synergistic effects of the two electrodes. The impressive results presented here may pave the way for promising applications in high energy density storage systems.

Abstract Asymmetric supercapacitor with high energy density has been developed successfully using graphene/MnO 2 composite as positive electrode and activated carbon nanofibers (ACN) as negative electrode in a neutral aqueous Na 2 SO 4 electrolyte. Due to the high capacitances and excellent rate performances of graphene/MnO 2 and ACN, as well as the synergistic effects of the two electrodes, such asymmetric cell exhibits superior electrochemical performances. An optimized asymmetric supercapacitor can be cycled reversibly in the voltage range of 0–1.8 V, and exhibits maximum energy density of 51.1 Wh kg −1 , which is much higher than that of MnO 2 //DWNT cell (29.1 Wh kg −1 ). Additionally, graphene/MnO 2 //ACN asymmetric supercapacitor exhibits excellent cycling durability, with 97% specific capacitance retained even after 1000 cycles. These encouraging results show great potential in developing energy storage devices with high energy and power densities for practical applications.

Abstract The development of low‐cost, efficient, and stable electrocatalysts for the oxygen reduction reaction (ORR) is desirable but remains a great challenge. Herein, we made a highly reactive and stable isolated single‐atom Fe/N‐doped porous carbon (ISA Fe/CN) catalyst with Fe loading up to 2.16 wt %. The catalyst showed excellent ORR performance with a half‐wave potential ( E 1/2 ) of 0.900 V, which outperformed commercial Pt/C and most non‐precious‐metal catalysts reported to date. Besides exceptionally high kinetic current density ( J k ) of 37.83 mV cm −2 at 0.85 V, it also had a good methanol tolerance and outstanding stability. Experiments demonstrated that maintaining the Fe as isolated atoms and incorporating nitrogen was essential to deliver the high performance. First principle calculations further attributed the high reactivity to the high efficiency of the single Fe atoms in transporting electrons to the adsorbed OH species.

Recently, convolutional neural networks have demonstrated excellent performance on various visual tasks, including the classification of common two-dimensional images. In this paper, deep convolutional neural networks are employed to classify hyperspectral images directly in spectral domain. More specifically, the architecture of the proposed classifier contains five layers with weights which are the input layer, the convolutional layer, the max pooling layer, the full connection layer, and the output layer. These five layers are implemented on each spectral signature to discriminate against others. Experimental results based on several hyperspectral image data sets demonstrate that the proposed method can achieve better classification performance than some traditional methods, such as support vector machines and the conventional deep learning-based methods.

Ultrathin, lightweight, and flexible electromagnetic-interference (EMI) shielding materials are urgently required to manage increasingly serious radiation pollution. 2D transition-metal carbides (MXenes) are considered promising alternatives to graphene for providing excellent EMI-shielding performance due to their outstanding metallic electrical conductivity. However, the hydrophilicity of MXene films may affect their stability and reliability when applied in moist or wet environments. Herein, for the first time, an efficient and facile approach is reported to fabricate freestanding, flexible, and hydrophobic MXene foam with reasonable strength by assembling MXene sheets into films followed by a hydrazine-induced foaming process. In striking contrast to well-known hydrophilic MXene materials, the MXene foams surprisingly exhibit hydrophobic surfaces and outstanding water resistance and durability. More interestingly, a much enhanced EMI-shielding effectiveness of ≈70 dB is achieved for the lightweight MXene foam as compared to its unfoamed film counterpart (53 dB) due to the highly efficient wave attenuation in the favorable porous structure. Therefore, the hydrophobic, flexible, and lightweight MXene foam with an excellent EMI-shielding performance is highly promising for applications in aerospace and portable and wearable smart electronics.

This review surveys recent advances in the applications of layered double hydroxides (LDHs) in heterogeneous catalysis. By virtue of the flexible tunability and uniform distribution of metal cations in the brucite-like layers and the facile exchangeability of intercalated anions, LDHs-both as directly prepared or after thermal treatment and/or reduction-have found many applications as stable and recyclable heterogeneous catalysts or catalyst supports for a variety of reactions with high industrial and academic importance. A major challenge in this rapidly growing field is to simultaneously improve the activity, selectivity and stability of these LDH-based materials by developing ways of tailoring the electronic structure of the catalysts and supports. Therefore, this Review article is mainly focused on the most recent developments in smart design strategies for LDH materials and the potential catalytic applications of the resulting materials.

Thanks to their remarkable mechanical, electrical, thermal, and barrier properties, graphene-based nanocomposites have been a hot area of research in the past decade. Because of their simple top-down synthesis, graphene oxide (GO) and reduced graphene oxide (rGO) have opened new possibilities for gas barrier, membrane separation, and stimuli-response characteristics in nanocomposites. Herein, we review the synthesis techniques most commonly used to produce these graphene derivatives, discuss how synthesis affects their key material properties, and highlight some examples of nanocomposites with unique and impressive properties. We specifically highlight their performances in separation applications, stimuli-responsive materials, anti-corrosion coatings, and energy storage. Finally, we discuss the outlook and remaining challenges in the field of practical industrial-scale production and use of graphene-derivative-based polymer nanocomposites. Keywords: Graphene oxide, Reduced graphene oxide, Graphene quantum dots polymer, Nanocomposites, Synthesis, Properties of graphene and graphene oxide, Applications

Diamonds are forever: A diamond-like framework in which the C–C bonds are replaced with rigid phenyl rings (see picture) is not only structurally stable but also has a large internal surface area. This porous aromatic framework (PAF-1) demonstrates high uptake capacities of hydrogen and carbon dioxide as well as benzene and toluene vapors, and has an unprecedented surface area of 7100 m2 g−1. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by 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.

Stable catalysts through steaming The lifetime of catalysts that convert automotive exhaust pollutants can be increased by lowering their operating temperature, which helps to prevent deactivation caused by the active metal atoms agglomerating into larger, less active particles. Nie et al. show that a thermally stable catalyst, atomically dispersed Pt 2+ on CeO 2 , can become active for CO oxidation at 150°C after steam treatment at 750°C. In studies with simulated vehicle exhaust, this catalyst treatment also improves its oxidation activity for other exhaust components such as hydrocarbons. Science , this issue p. 1419

Study of flexible nanodielectric materials (FNDMs) with high permittivity is one of the most active academic research areas in advanced functional materials. FNDMs with excellent dielectric properties are demonstrated to show great promise as energy-storage dielectric layers in high-performance capacitors. These materials, in common, consist of nanoscale particles dispersed into a flexible polymer matrix so that both the physical/chemical characteristics of the nanoparticles and the interaction between the nanoparticles and the polymers have crucial effects on the microstructures and final properties. This review first outlines the crucial issues in the nanodielectric field and then focuses on recent remarkable research developments in the fabrication of FNDMs with special constitutents, molecular structures, and microstructures. Possible reasons for several persistent issues are analyzed and the general strategies to realize FNDMs with excellent integral properties are summarized. The review further highlights some exciting examples of these FNDMs for power-energy-storage applications.

Ionic liquids (ILs) are normally defined as compounds completely composed of ions with melting point below 100 °C. The first IL (ethylammonium nitrate) was reported by Paul Walden in 1914, who at that time never realized that ILs would become a major scientific area after almost one century. Actually, ILs as innovative fluids have received wide attention only during the past two decades. The number of SCI papers published on ILs has exponentially increased from a few in 1996 to >5000 in 2016, exceeding the annual growth rates of other popular scientific areas. This indicates that more and more researchers are engaged in studying this exciting area, with the outcomes being plentiful. A multidisciplinary study on ILs is emerging, including chemistry, materials science, chemical engineering, and environmental science. More specifically, some important fundamental viewpoints are now different from the original concepts, as insights into the nature of ILs become deeper. For example, the physicochemical properties of ILs are now recognized as ranging broadly from the oft quoted “nonvolatile, non-flammable, and air and water stable” to those that are distinctly volatile, flammable, and unstable. This is attributed to numerous combinations of cations and anions that meet the definition of ILs, leading to a diverse suite of behaviors. Regardless, ILs remain more desirable than conventional volatile solvents and/or catalysts in many physical and chemical processes, often exhibiting “green” and “designer” properties to a useful degree.

Development of a non-noble-metal hydrogen-producing catalyst is essential to the development of solar water-splitting devices. Improving both the activity and the stability of the catalyst remains a key challenge. In this Communication, we describe a two-step reaction for preparing three-dimensional electrodes composed of CoSe2 nanoparticles grown on carbon fiber paper. The electrode exhibits excellent catalytic activity for a hydrogen evolution reaction in an acidic electrolyte (100 mA/cm(2) at an overpotential of ∼180 mV). Stability tests though long-term potential cycles and extended electrolysis confirm the exceptional durability of the catalyst. This development offers an attractive catalyst material for large-scale water-splitting technology.

2D transition metal carbides, nitrides, and carbonitrides, also known as MXenes, are versatile materials due to their adjustable structure and rich surface chemistry. The physical and chemical diversity has recognized MXenes as a potential 2D material with a wide spectrum of application domains. Since the discovery of MXenes in 2011, a wide variety of synthetic routes has been proposed with advancement toward large-scale preparing methods for MXene nanosheets and derivative products. Herein, the critical synthesis aspects and the operating conditions that influence the physical and chemical characteristics of MXenes are discussed in detail. The emerging etching methods including HF etching methods, in situ HF-forming etching methods, electrochemical etching methods, alkali etching methods, and molten salt etching methods, as well as delamination strategies are discussed. Considering the future developments and practical applications, the large-scale synthesis routes and the antioxidation strategies of MXenes are also summarized. In summary, a generalized overview of MXenes synthesis protocols with an outlook for the current challenges and promising technologies for large-scale preparation and stable storage is provided.

Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth's radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.

Developing efficient catalysts for nitrogen fixation is becoming increasingly important but is still challenging due to the lack of robust design criteria for tackling the activity and selectivity problems, especially for electrochemical nitrogen reduction reaction (NRR). Herein, by means of large-scale density functional theory (DFT) computations, we reported a descriptor-based design principle to explore the large composition space of two-dimensional (2D) biatom catalysts (BACs), namely, metal dimers supported on 2D expanded phthalocyanine (M2-Pc or MM′-Pc), toward the NRR at the acid conditions. We sampled both homonuclear (M2-Pc) and heteronuclear (MM′-Pc) BACs and constructed the activity map of BACs by using N2H* adsorption energy as the activity descriptor, which reduces the number of promising catalyst candidates from over 900 to less than 100. This strategy allowed us to readily identify 3 homonuclear and 28 heteronuclear BACs, which could break the metal-based activity benchmark toward the efficient NRR. Particularly, using the free energy difference of H* and N2H* as a selectivity descriptor, we screened out five systems, including Ti2-Pc, V2-Pc, TiV-Pc, VCr-Pc, and VTa-Pc, which exhibit a strong capability of suppressing the competitive hydrogen evolution reaction (HER) with favorable limiting potential of −0.75, −0.39, −0.74, −0.85, and −0.47 V, respectively. This work not only broadens the possibility of discovering more efficient BACs toward N2 fixation but also provides a feasible strategy for rational design of NRR electrocatalysts and helps pave the way to fast screening and design of efficient BACs for the NRR and other electrochemical reactions.

Functional polymethylmethacrylate (PMMA)/graphene nanocomposite microcellular foams were prepared by blending of PMMA with graphene sheets followed by foaming with subcritical CO(2) as an environmentally benign foaming agent. The addition of graphene sheets endows the insulating PMMA foams with high electrical conductivity and improved electromagnetic interference (EMI) shielding efficiency with microwave absorption as the dominant EMI shielding mechanism. Interestingly, because of the presence of the numerous microcellular cells, the graphene-PMMA foam exhibits greatly improved ductility and tensile toughness compared to its bulk counterpart. This work provides a promising methodology to fabricate tough and lightweight graphene-PMMA nanocomposite microcellular foams with superior electrical and EMI shielding properties by simultaneously combining the functionality and reinforcement of the graphene sheets and the toughening effect of the microcellular cells.