Tianjin University of Technology

We develop an N-coordination strategy to design a robust CO2 reduction reaction (CO2RR) electrocatalyst with atomically dispersed Co–N5 site anchored on polymer-derived hollow N-doped porous carbon spheres. Our catalyst exhibits high selectivity for CO2RR with CO Faradaic efficiency (FECO) above 90% over a wide potential range from −0.57 to −0.88 V (the FECO exceeded 99% at −0.73 and −0.79 V). The CO current density and FECO remained nearly unchanged after electrolyzing 10 h, revealing remarkable stability. Experiments and density functional theory calculations demonstrate single-atom Co–N5 site is the dominating active center simultaneously for CO2 activation, the rapid formation of key intermediate COOH* as well as the desorption of CO.

Comprehensive summary of the progress including crystal structures, fabrication methods, applications (especially for electronics) and functionalization of 2D-hBN from its discovery.

Arylamine organic dyes with donor (D), π-bridge (π) and acceptor (A) moieties for dye-sensitized solar cells (DSCs) have received great attention in the last decade because of their high molar absorption coefficient, low cost and structural variety. In the early stages, the efficiency of DSCs with arylamine organic dyes with D-π-A character was far behind that of DSCs with ruthenium(II) complexes partly due to the lack of information about the relationship between the chemical structures and the photovoltaic performance. However, exciting progress has been recently made, and power conversion efficiencies over 10% were obtained for DSCs with arylamine organic dyes. It is thus that the recent research and development in the field of arylamine organic dyes employing an iodide/triiodide redox couple or polypyridyl cobalt redox shuttles as the electrolytes for either DSCs or solid-state DSCs has been summarized. The cell performance of the arylamine organic dyes are compared, providing a comprehensive overview of arylamine organic dyes, demonstrating the advantages/disadvantages of each class, and pointing out the field that needs to reinforce the research direction in the further application of DSCs.

Significance Electrolysis of water to generate hydrogen fuel could be vital to the future renewable energy landscape. Electrodes that can sustain seawater splitting without chloride corrosion could address the issue of freshwater scarcity on Earth. Herein, a hierarchical anode consisting of a nickel–iron hydroxide electrocatalyst layer uniformly coated on a sulfide layer formed on Ni substrate was developed, affording superior catalytic activity and corrosion resistance in seawater electrolysis. In situ-generated polyanion-rich passivating layers formed in the anode are responsible for chloride repelling and high corrosion resistance, leading to new directions for designing and fabricating highly sustained seawater-splitting electrodes and providing an opportunity to use the vast seawater on Earth as an energy carrier.

By decomposing the visual tracking task into two subproblems as classification for pixel category and regression for object bounding box at this pixel, we propose a novel fully convolutional Siamese network to solve visual tracking end-to-end in a per-pixel manner. The proposed framework SiamCAR consists of two simple subnetworks: one Siamese subnetwork for feature extraction and one classification-regression subnetwork for bounding box prediction. Different from state-of-the-art trackers like Siamese-RPN, SiamRPN++ and SPM, which are based on region proposal, the proposed framework is both proposal and anchor free. Consequently, we are able to avoid the tricky hyper-parameter tuning of anchors and reduce human intervention. The proposed framework is simple, neat and effective. Extensive experiments and comparisons with state-of-the-art trackers are conducted on challenging benchmarks including GOT-10K, LaSOT, UAV123 and OTB-50. Without bells and whistles, our SiamCAR achieves the leading performance with a considerable real-time speed. The code is available at https://github.com/ohhhyeahhh/SiamCAR.

Solution-processable functionalized graphene (SPFGraphene, see figure) is used as the electron-accepting material in organic photovoltaic (OPV) devices for the first time, showing that it is a competitive alternative. The fabrication and performance of bulk heterojunction OPV devices with SPFGraphene and different donor materials is presented, together with the impact of post-fabrication annealing.

Polymerization of glycinamide-conjugated monomer alone in concentrated aqueous solution enables facile formation of a mechanically strong and a highly stable supramolecular polymer (SP) hydrogel because of the cooperatively hydrogen-bonded crosslinking and strengthening effect from dual amide motifs. This SP hydrogel exhibits thermoplastic processability, injectability, and self-reparability because of the dynamic destruction and reconstruction of hydrogen bonds in response to temperature change. 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.

Distinguished by particular physical and chemical properties, metal oxide materials have been a focus of research and exploitation for applications in energy storage devices. Used as supercapacitor electrode materials, metal oxides have certified attractive performances for fabricating various supercapacitor devices in a broad voltage window. In comparison with single metal oxides, bimetallic oxide materials are highly desired for overcoming the constraint of the poor electric conductivity of single metal oxide materials, achieving a high capacitance and raising the energy density at this capacitor-level power. Herein, we investigate the principal elements affecting the properties of bimetallic oxide electrodes to reveal the relevant energy storage mechanisms. Thus, the influences of the chemical constitution, structural features, electroconductivity, oxygen vacancies and various electrolytes in the electrochemical behavior are discussed. Moreover, the progress, development and improvement of multifarious devices are emphasized systematically, covering from an asymmetric to hybrid configuration, and from aqueous to non-aqueous systems. Ultimately, some obstinate and unsettled issues are summarized as well as a prospective direction has been given on the future of metal oxide-based supercapacitors.

Abstract Improving the stability of lead halide perovskite quantum dots (QDs) in a system containing water is the key for their practical application in artificial photosynthesis. Herein, we encapsulate low‐cost CH 3 NH 3 PbI 3 (MAPbI 3 ) perovskite QDs in the pores of earth‐abundant Fe‐porphyrin based metal organic framework (MOF) PCN‐221(Fe x ) by a sequential deposition route, to construct a series of composite photocatalysts of MAPbI 3 @PCN‐221(Fe x ) ( x =0–1). Protected by the MOF the composite photocatalysts exhibit much improved stability in reaction systems containing water. The close contact of QDs to the Fe catalytic site in the MOF, allows the photogenerated electrons in the QDs to transfer rapidly the Fe catalytic sites to enhance the photocatalytic activity for CO 2 reduction. Using water as an electron source, MAPbI 3 @PCN‐221(Fe 0.2 ) exhibits a record‐high total yield of 1559 μmol g −1 for photocatalytic CO 2 reduction to CO (34 %) and CH 4 (66 %), 38 times higher than that of PCN‐221(Fe 0.2 ) in the absence of perovskite QDs.

Noble-metal alloys are widely used as heterogeneous catalysts. However, due to the existence of scaling properties of adsorption energies on transition metal surfaces, the enhancement of catalytic activity is frequently accompanied by side reactions leading to a reduction in selectivity for the target product. Herein, we describe an approach to breaking the scaling relationship for propane dehydrogenation, an industrially important reaction, by assembling single atom alloys (SAAs), to achieve simultaneous enhancement of propylene selectivity and propane conversion. We synthesize γ-alumina-supported platinum/copper SAA catalysts by incipient wetness co-impregnation method with a high copper to platinum ratio. Single platinum atoms dispersed on copper nanoparticles dramatically enhance the desorption of surface-bounded propylene and prohibit its further dehydrogenation, resulting in high propylene selectivity (~90%). Unlike previous reported SAA applications at low temperatures (<400 °C), Pt/Cu SAA shows excellent stability of more than 120 h of operation under atmospheric pressure at 520 °C.

With the inspiration of developing bifunctional electrode materials for reversible oxygen electrocatalysis, one strategy of heteroatom doping is proposed to fabricate dual metal single-atom catalysts. However, the identification and mechanism functions of polynary single-atom structures remain elusive. Atomically dispersed binary Co-Ni sites embedded in N-doped hollow carbon nanocubes (denoted as CoNi-SAs/NC) are synthesized via proposed pyrolysis of dopamine-coated metal-organic frameworks. The atomically isolated bimetallic configuration in CoNi-SAs/NC is identified by combining microscopic and spectroscopic techniques. When employing as oxygen electrocatalysts in alkaline medium, the resultant CoNi-SAs/NC hybrid manifests outstanding catalytic performance for bifunctional oxygen reduction/evolution reactions, boosting the realistic rechargeable zinc-air batteries with high efficiency, low overpotential, and robust reversibility, superior to other counterparts and state-of-the-art precious-metal catalysts. Theoretical computations based on density functional theory demonstrate that the homogenously dispersed single atoms and the synergistic effect of neighboring Co-Ni dual metal center can optimize the adsorption/desorption features and decrease the overall reaction barriers, eventually promoting the reversible oxygen electrocatalysis. This work not only sheds light on the controlled synthesis of atomically isolated advanced materials, but also provides deeper understanding on the structure-performance relationships of nanocatalysts with multiple active sites for various catalytic applications.

Graphitic carbon nitride (g‐C 3 N 4 ) has recently emerged as an attractive photocatalyst for solar energy conversion. However, the photocatalytic activities of g‐C 3 N 4 remain moderate because of the insufficient solar‐light absorption and the fast electron–hole recombination. Here, defect‐modified g‐C 3 N 4 (DCN) photocatalysts, which are easily prepared under mild conditions and show much extended light absorption with band gaps decreased from 2.75 to 2.00 eV, are reported. More importantly, cyano terminal CN groups, acting as electron acceptors, are introduced into the DCN sheet edge, which endows the DCN with both n‐ and p‐type conductivities, consequently giving rise to the generation of p–n homojunctions. This homojunction structure is demonstrated to be highly efficient in charge transfer and separation, and results in a fivefold enhanced photocatalytic H 2 evolution activity. The findings deepen the understanding on the defect‐related issues of g‐C 3 N 4 ‐based materials. Additionally, the ability to build homojunction structures by the defect‐induced self‐functionalization presents a promising strategy to realize precise band engineering of g‐C 3 N 4 and related polymer semiconductors for more efficient solar energy conversion applications.

Abstract Dry reforming of methane (DRM) is an attractive route to utilize CO 2 as a chemical feedstock with which to convert CH 4 into valuable syngas and simultaneously mitigate both greenhouse gases. Ni-based DRM catalysts are promising due to their high activity and low cost, but suffer from poor stability due to coke formation which has hindered their commercialization. Herein, we report that atomically dispersed Ni single atoms, stabilized by interaction with Ce-doped hydroxyapatite, are highly active and coke-resistant catalytic sites for DRM. Experimental and computational studies reveal that isolated Ni atoms are intrinsically coke-resistant due to their unique ability to only activate the first C-H bond in CH 4 , thus avoiding methane deep decomposition into carbon. This discovery offers new opportunities to develop large-scale DRM processes using earth abundant catalysts.

Cycling 2D crystal growth The electronic and optical properties of two-dimensional (2D) transitional metal dichalcogenides such as MoS 2 and WSe 2 could be modulated by creating in-plane superlattices and heterostructures from these materials. However, single layers of these materials are fragile and often do not withstand the processing conditions needed during subsequent growth steps. Zhang et al. developed a reverse-flow reactor that avoids thermal degradation and unwanted crystal nucleation. They demonstrate several examples of block-by-block epitaxial growth, such as 2D heterostructures where MoS 2 surrounds a WS 2 core and superlattices where the composition alternates between WS 2 and WSe 2 . Science , this issue p. 788

Platinum-based nanocatalysts play a crucial role in various electrocatalytic systems that are important for renewable, clean energy conversion, storage and utilization. However, the scarcity and high cost of Pt seriously limit the practical application of these catalysts. Decorating Pt catalysts with other transition metals offers an effective pathway to tailor their catalytic properties, but often at the sacrifice of the electrochemical active surface area (ECSA). Here we report a single-atom tailoring strategy to boost the activity of Pt nanocatalysts with minimal loss in surface active sites. By starting with PtNi alloy nanowires and using a partial electrochemical dealloying approach, we create single-nickel-atom-modified Pt nanowires with an optimum combination of specific activity and ECSA for the hydrogen evolution, methanol oxidation and ethanol oxidation reactions. The single-atom tailoring approach offers an effective strategy to optimize the activity of surface Pt atoms and enhance the mass activity for diverse reactions, opening a general pathway to the design of highly efficient and durable precious metal-based catalysts. Platinum plays a crucial role in various electrocatalytic systems, but its scarcity and cost limit its practical application. Now, a single-atom tailoring strategy applied to platinum nanowires maximizes their specific and mass activities for the hydrogen evolution and methanol and ethanol oxidation reactions.

The search for a low-cost, ultrastable, and highly efficient non-precious metal catalyst substitute for Pt in the oxygen reduction reaction (ORR) is extremely urgent, especially in acidic media. Herein, we develop a template-assisted pyrolysis (TAP) method to obtain a unique Co catalyst with isolated single atomic sites anchored on hollow N-doped carbon spheres (ISAS-Co/HNCS). Both the single sites and the hollow substrate endow the catalyst with excellent ORR performance. The half-wave potential in acidic media approaches that of Pt/C. Experiments and density functional theory have verified that isolated Co sites are the source for the high ORR activity because they significantly increase the hydrogenation of OH* species. This TAP method is also demonstrated to be effective in preparing a series of ISAS-M/HNCS, which provides opportunities for discovering new catalysts.

Abstract A competitive complexation strategy has been developed to construct a novel electrocatalyst with Zn‐Co atomic pairs coordinated on N doped carbon support (Zn/CoN‐C). Such architecture offers enhanced binding ability of O 2 , significantly elongates the O−O length (from 1.23 Å to 1.42 Å), and thus facilitates the cleavage of O−O bond, showing a theoretical overpotential of 0.335 V during ORR process. As a result, the Zn/CoN‐C catalyst exhibits outstanding ORR performance in both alkaline and acid conditions with a half‐wave potential of 0.861 and 0.796 V respectively. The in situ XANES analysis suggests Co as the active center during the ORR. The assembled zinc–air battery with Zn/CoN‐C as cathode catalyst presents a maximum power density of 230 mW cm −2 along with excellent operation durability. The excellent catalytic activity in acid is also verified by H 2 /O 2 fuel cell tests (peak power density of 705 mW cm −2 ).

Engineering the surface structure at the atomic level can be used to precisely and effectively manipulate the reactivity and durability of catalysts. Here we report tuning of the atomic structure of one-dimensional single-crystal cobalt (II) oxide (CoO) nanorods by creating oxygen vacancies on pyramidal nanofacets. These CoO nanorods exhibit superior catalytic activity and durability towards oxygen reduction/evolution reactions. The combined experimental studies, microscopic and spectroscopic characterization, and density functional theory calculations reveal that the origins of the electrochemical activity of single-crystal CoO nanorods are in the oxygen vacancies that can be readily created on the oxygen-terminated {111} nanofacets, which favourably affect the electronic structure of CoO, assuring a rapid charge transfer and optimal adsorption energies for intermediates of oxygen reduction/evolution reactions. These results show that the surface atomic structure engineering is important for the fabrication of efficient and durable electrocatalysts.

Abstract NH 3 synthesis by the electrocatalytic N 2 reduction reaction (NRR) under ambient conditions is an appealing alternative to the currently employed industrial method—the Haber–Bosch process—that requires high temperature and pressure. We report single Mo atoms anchored to nitrogen‐doped porous carbon as a cost‐effective catalyst for the NRR. Benefiting from the optimally high density of active sites and hierarchically porous carbon frameworks, this catalyst achieves a high NH 3 yield rate (34.0±3.6 μg h −1 mg cat. −1 ) and a high Faradaic efficiency (14.6±1.6 %) in 0.1 m KOH at room temperature. These values are considerably higher compared to previously reported non‐precious‐metal electrocatalysts. Moreover, this catalyst displays no obvious current drop during a 50 000 s NRR, and high activity and durability are achieved in 0.1 m HCl. The findings provide a promising lead for the design of efficient and robust single‐atom non‐precious‐metal catalysts for the electrocatalytic NRR.

Abstract Surface-supported isolated atoms in single-atom catalysts (SACs) are usually stabilized by diverse defects. The fabrication of high-metal-loading and thermally stable SACs remains a formidable challenge due to the difficulty of creating high densities of underpinning stable defects. Here we report that isolated Pt atoms can be stabilized through a strong covalent metal-support interaction (CMSI) that is not associated with support defects, yielding a high-loading and thermally stable SAC by trapping either the already deposited Pt atoms or the PtO 2 units vaporized from nanoparticles during high-temperature calcination. Experimental and computational modeling studies reveal that iron oxide reducibility is crucial to anchor isolated Pt atoms. The resulting high concentrations of single atoms enable specific activities far exceeding those of conventional nanoparticle catalysts. This non defect-stabilization strategy can be extended to non-reducible supports by simply doping with iron oxide, thus paving a new way for constructing high-loading SACs for diverse industrially important catalytic reactions.