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Heterogeneous cobalt-based catalysts are highly effective in activing peroxymonosulfate (PMS) and produce free radicals to deal with recalcitrant organic pollutants in water. However, unfeasible recyclability and gradual performance degradation remain challenging due to the easy agglomeration and leaching of active cobalt species. Herein, a strategy is proposed to construct stably anchored and highly dispersed Co 2+ sites on dual functional sulfonated covalent organic frameworks (COF-Co). The sulfonic acid groups are able to realize the targeted binding with cobalt ions through a two-step cation-exchange method, leading to strong combination with active Co 2+ sites and utmost utilization efficiencies. Moreover, the super-hydrophility of sulfonic acid groups favors the rapid accessibility of organic molecules to the catalyst and accelerates the degradation. Remarkably, COF-Co exhibits high activity in PMS activation, effective oxidation for tetracycline degradation (92% within 30 min at 30 mg L -1 ) and other coloring contaminants, and excellent recycle stability. This work can guide the rational design of efficient and environmentally friendly PMS-activated catalyst with great potential for application in wastewater treatment., (© 2024 Wiley‐VCH GmbH.)

The electrochemical synthesis of hydrogen peroxide from oxygen and water, powered by renewable electricity, provides a highly attractive alternative to the energy-intensive autoxidation process presently used in industry, but much remains unknown about this two-electron oxygen reduction reaction (2e-ORR), especially the local proton effect. Here, we have investigated the function of hydrogen-associated intermediates in the 2e-ORR using a rationally designed cooperative electrode material with cobalt (II) clusters embedded onto the oxidized carbon nanotube composites (Co-OCNT). We found that the local proton availability can determine both the reaction kinetics and selectivity. A 2e-ORR process involving hydrogen radical transfer is confirmed. Specifically, the carbon sites from the OCNTs promote proton production, and the cobalt sites from the Co cluster facilitate ORR intermediate formation. The high local proton availability and the cooperative dual-active sites both contribute to the superior reaction kinetics and selectivity of the Co-OCNT, reaching an H 2 O 2 production rate of ~40.6 mol g cat -1  h -1 and a faradaic efficiency of 90 % at a current density of 300 mA cm -2 . Further cascading the 2e-ORR with the electro-Fenton process shows a high selectivity of oxalic acid up to 97 % for the valorization of ethylene glycol., (© 2024 Wiley-VCH GmbH.)

Rechargeable sodium chloride (Na-Cl 2 ) batteries have emerged as promising alternatives for next-generation energy storage due to their superior energy density and sodium abundance. However, their practical applications are hindered by the sluggish chlorine cathode kinetics related to the aggregation of NaCl and its difficult transformation into Cl 2 . Herein, the study, for the first time from the perspective of electrode level in Na-Cl 2 batteries, proposes a free-standing carbon cathode host with customized vertical channels to facilitate the SOCl 2 transport and regulate the NaCl deposition. Accordingly, electrode kinetics are significantly enhanced, and the deposited NaCl is distributed evenly across the whole electrode, avoiding the blockage of pores in the carbon host, and facilitating its oxidation to Cl 2. With this low-polarization cathode, the Na-Cl 2 batteries can deliver a practically high areal capacity approaching 4 mAh cm -2 and a long cycle life of over 170 cycles. This work demonstrates the significance of pore engineering in electrodes for mediating chlorine conversion kinetics in rechargeable alkali-metal-Cl 2 batteries., (© 2024 Wiley‐VCH GmbH.)

Silicon is attractive for lithium-ion batteries and beyond but suffers large volume change upon cycling. Hierarchical tactics show promise yet lack control over the unit construction and arrangement, limiting stability improvement at the practical level. Here, a protocol is developed as controlled isotropic canalization of microsized silicon. Distinct from the existing strategies, it involves isotropic canalization by honeycomb-like radial arrangement of silicon nanosheets, and canal consolidation by controlled dual bonding of silicon with carbon. The proof-of-concept nitrogen-doped carbon dual-bonded silicon honeycomb-like microparticles, specifically with a medium density of CNSi and COSi bonds, exhibit stable cycling impressively at high rates and industrial-scale loadings. Two key issues involve isotropic canalization facilitating ion transport in all directions of individual granules and controlled consolidation conferring selective ion permeation and securing charge transport. The study highlights the configurational isotropy and interfacial bonding density, and provides insight into rational design and manufacture of silicon and others with industry-viable features., (© 2023 Wiley-VCH GmbH.)

Carbon-rich materials have drawn tremendous attention toward a wide spectrum of energy applications due to their superior electronic mobility, good mechanical strength, ultrahigh surface area, and more importantly, abundant diversity in structure and components. Herein, rationally designed and bottom-up constructed carbon-rich materials for energy storage and conversion are discussed. The fundamental design principles are itemized for the targeted preparation of carbon-rich materials and the latest remarkable advances are summarized in terms of emerging dimensions including sp 2 carbon fragment manipulation, pore structure modulation, topological defect engineering, heteroatom incorporation, and edge chemical regulation. In this respect, the corresponding structure-property relationships of the resultant carbon-rich materials are comprehensively discussed. Finally, critical perspectives on future challenges of carbon-rich materials are presented. The progress highlighted here will provide meaningful guidance on the precise design and targeted synthesis of carbon-rich materials, which are of critical importance for the achievement of performance characteristics highly desirable for urgent energy deployment., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Schiff-base networks (SBNs), as typical examples of nitrogen-doped microporous organic polymers (MOPs), exhibit promising application prospects owing to their stable properties and tunable chemical structures. However, their band structure engineering, which plays a key role in optical properties, remains elusive due to the complicated mechanisms behind energy level adjustment. In this work, a series of SBNs are fabricated by tailoring the ratio of p-phthalaldehyde and o-phthalaldehyde in the Schiff-base chemistry reaction with melamine, resulting in a straightforward as well as continuous tuning of their band gaps ranging from 4.4 to 1.4 eV. Consequently, SBNs can be successfully used as photocatalysts with excellent visible-light photocatalytic activity even under metal-free conditions. Significantly, electronic structures of SBNs are systematically studied by electrochemical and spectroscopic characterizations, demonstrating that the enhanced performance is ascribed to proper band structure and improved charge separation ability. More importantly, in combination with theoretical calculations, the band structure regulation mechanism and band structure-photocatalytic property relationship are deeply disclosed. The results obtained from this study will not only furnish SBN materials with excellent performance for solar energy conversion, but also open up elegant protocols for the molecular engineering of MOPs with desirable band structures., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Building stable and efficient electron and ion transport pathways are critically important for energy storage electrode materials and systems. Herein, a scallop-inspired shell engineering strategy is proposed and demonstrated to confine high volume change silicon microparticles toward the construction of stable and high volumetric capacity binder-free lithium battery anodes. As for each silicon microparticle, the methodology involves an inner sealed but adaptable overlapped graphene shell, and an outer open hollow shell consisting of interconnected reduced graphene oxide, mimicking the scallop structure. The inner closed shell enables simultaneous stabilization of the interfaces of silicon with both carbon and electrolyte, substantially facilitates efficient and rapid transport of both electrons and lithium ions from/to silicon, the outer open hollow shell creates stable and robust transport paths of both electrons and lithium ions throughout the electrode without any sophisticated additives. The resultant self-supported electrode has achieved stable cycling with rapidly increased coulombic efficiency in the early stage, superior rate capability, and remarkably high volumetric capacity upon a facile pressing process. The rational design and engineering of graphene shells of the silicon microparticles developed can provide guidance for the development of a wide range of other high capacity but large volume change electrochemically active materials., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

To improve the electrochemical performance of carbonaceous anodes for lithium ion batteries (LIBs), the incorporation of both well-defined heteroatom species and the controllable 3D porous networks are urgently required. In this work, a novel N-enriched carbon/carbon nanotube composite (NEC/CNT) through a chemically induced precursor-controlled pyrolysis approach is developed. Instead of conventional N-containing sources or precursors, Schiff-base network (SNW-1) enables the desirable combination of a 3D polymer with intrinsic microporosity and ultrahigh N-content, which can significantly promote the fast transport of both Li + and electron. Significantly, the strong interaction between carbon skeleton and nitrogen atoms enables the retention of ultrahigh N-content up to 21 wt% in the resultant NEC/CNT, which exhibits a super-high capacity (1050 mAh g -1 ) for 1000 cycles and excellent rate performance (500 mAh g -1 at a current density of 5 A g -1 ) as the anode material for LIBs. The NEC/CNT composite affords a new model system as well as a totally different insight for deeply understanding the relationship between chemical structures and lithium ion storage properties, in which chemistry may play a more important role than previously expected., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Bendable energy-storage systems with high energy density are demanded for conformal electronics. Lithium-metal batteries including lithium-sulfur and lithium-oxygen cells have much higher theoretical energy density than lithium-ion batteries. Reckoned as the ideal anode, however, Li has many challenges when directly used, especially its tendency to form dendrite. Under bending conditions, the Li-dendrite growth can be further aggravated due to bending-induced local plastic deformation and Li-filaments pulverization. Here, the Li-metal anodes are made bending tolerant by integrating Li into bendable scaffolds such as reduced graphene oxide (r-GO) films. In the composites, the bending stress is largely dissipated by the scaffolds. The scaffolds have increased available surface for homogeneous Li plating and minimize volume fluctuation of Li electrodes during cycling. Significantly improved cycling performance under bending conditions is achieved. With the bending-tolerant r-GO/Li-metal anode, bendable lithium-sulfur and lithium-oxygen batteries with long cycling stability are realized. A bendable integrated solar cell-battery system charged by light with stable output and a series connected bendable battery pack with higher voltage is also demonstrated. It is anticipated that this bending-tolerant anode can be combined with further electrolytes and cathodes to develop new bendable energy systems., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Lithium-sulfur (Li-S) battery has emerged as one of the most promising next-generation energy-storage systems. However, the shuttle effect greatly reduces the battery cycle life and sulfur utilization, which is great deterrent to its practical use. This paper reviews the tremendous efforts that are made to find a remedy for this problem, mostly through physical or chemical confinement of the lithium polysulfides (LiPSs). Intrinsically, this "confinement" has a relatively limited effect on improving the battery performance because in most cases, the LiPSs are "passively" blocked and cannot be reused. Thus, this strategy becomes less effective with a high sulfur loading and ultralong cycling. A more "positive" method that not only traps but also increases the subsequent conversion of LiPSs back to lithium sulfides is urgently needed to fundamentally solve the shuttle effect. Here, recent advances on catalytic effects in increasing the rate of conversion of soluble long-chain LiPSs to insoluble short-chain Li 2 S 2 /Li 2 S, and vice versa, are reviewed, and the roles of noble metals, metal oxides, metal sulfides, metal nitrides, and some metal-free materials in this process are highlighted. Challenges and potential solutions for the design of catalytic cathodes and interlayers in Li-S battery are discussed in detail.

A facile roll-to-roll method is developed for fabricating reduced graphene oxide (rGO)-based flexible transparent conductive films. A Sn 2+ /ethanol reduction system and a rationally designed fast coating-drying-washing technique are proven to be highly efficient for low-cost continuous production of large-area rGO films and patterned rGO films, extremely beneficial toward the manufacture of flexible photoelectronic devices., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A bottom-up method is used to construct novel metal-free catalysts for deeper study of oxygen reduction reaction (ORR) catalysis. Through controlling the structural evolution of a 2D covalent triazine-based framework, the conductivity, nitrogen configurations, and multidoping structures of the as-prepared catalysts can be easily tuned, which makes a great platform for both studying the mechanisms of the ORR and optimizing the performances of the metal-free catalysts., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Graphene-sheet-supported uniform ultrasmall (≈3 nm) silicon quantum dots have been successfully synthesized by a simple and effective self-assembly strategy, exhibiting unprecedented fast, surface-controlled lithium-storage behavior and outstanding lithium-storage properties including extraordinary rate capability and remarkable cycling stability, attributable to the intrinsic role of approaching the downsizing limit of silicon., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel Au@MnO2 supercapacitor is presented. The sophisticated core-shell architecture combining an Au nanomesh core with a MnO2 shell on a flexible polymeric substrate is demonstrated as an electrode for high performance transparent flexible supercapacitors (TFSCs). Due to their unique structure, high areal/gravimetric capacitance and rate capability for TFSCs are achieved., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A key to improve the electrochemical performance of energy storage systems (e.g., lithium ion batteries and supercapacitors) is to develop advanced electrode materials. In the last few years, although originating from the unique structure and property of graphene, interest has expanded beyond the originally literally defined graphene into versatile integration of numerous intermediate structures lying between graphene and organic polymer, particularly for the development of new electrode materials for energy storage devices. Notably, diverse designations have shaded common characteristics of the molecular configurations of these newly-emerging materials, severely impeding the design, synthesis, tailoring, functionalization, and control of functional electrode materials in a rational and systematical manner. This concept paper highlights all these intermediate materials, specifically comprising graphene subunits intrinsically interconnected by organic linkers or fractions, following a general concept of graphenal polymers. Combined with recent advances made by our group and others, two representative synthesis approaches (bottom-up and top-down) for graphenal polymers are outlined, as well as the structure-property relationships of these graphenal polymers as energy storage electrode materials are discussed., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Both of the arrays of Cu₂S nanowires and the superlattices of Cu₂S nanoparticles are obtained by the solventless thermolysis of copper thiolate in the presence of laurate. For the first time, the types of anions in the reaction system, which are generally neglected in previous studies, are found to determine the structure of the final assembly products. Furthermore, experimental results shows in the presence of Cl⁻ ions, Cl⁻ ions participate in the self-assembly process and promote the formation of Cu₂S nanowire arrays. Finally, the content of Cl⁻ ions is gradually decreased with assembly reaction proceeding. Therefore, duiring the process, Cl⁻ ions play a role of 'catassembly' in the formation of Cu₂S nanocrystal superstructures., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Supercapacitors have been widely studied around the world in recent years, due to their excellent power density and long cycle life. As the most frequently used electrode materials for supercapacitors, carbonaceous materials attract more and more attention. However, their relatively low energy density still holds back the widespread application. Up to now, various strategies have been developed to figure out this problem. This research news summarizes the recent advances in improving the supercapacitor performance of carbonaceous materials, including the incorporation of heteroatoms and the pore size effect (subnanopores' contribution). In addition, a new class of carbonaceous materials, porous organic networks (PONs) has been managed into the supercapacitor field, which promises great potential in not only improving the supercapacitor performances, but also unraveling the related mechanisms., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A scalable, low-cost and environmentally benign strategy is developed for the facile construction of a unique kind of three-dimensional porous electrode architecture for high-performance lithium ion batteries. The methodology is based on the employment of pyrolyzed bacterial cellulose as a new three-dimensional porous scaffold to support various nanostructured active electrode materials, such as SnO2 and Ge., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel catalyst composed of a microporous polyphenylene network and covalently stabilized Pd clusters (Pd/MPP) for highly efficient Suzuki-Miyaura coupling is synthesized with an in-situ one-pot chemical approach, through the catalytic trimerization of 1,3,5-triethynylbenzene. The unique Pd/MPP cluster exhibits very high catalytic activity for a broad scope of Suzuki-Miyaura reactions with short reaction time, good yield, and high turnover number and turnover frequency values, even in aqueous media under aerobic conditions. The strong covalent interaction between Pd and MPP network prevents the agglomeration or leaching of Pd clusters and enables the catalyst to remain highly active, even after a number of cycles., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel anode structure composed of silicon nanowires dwelling in graphitic tubes is developed. The thus-fabricated 1D/1D hybrid structure exhibits good rate capability and remarkable cycling stability, which mainly originates from their structural advantages including the built-in void spaces and the robust line-to-line contact mode between the components., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An innovative approach is developed for the high-throughput, large-area, and low-cost fabrication of reduced graphene oxide (RGO) nanoribbon networks by using electrospun polymer-based nanowires as the etching mask. Combined with their tunable, controllable structures and transmittance/conductivity properties, the as-fabricated RGO nanoribbon networks exhibit potential as transparent conductive film electrodes, for example, in electrochromic devices., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The assembly of graphene derivatives and inorganic nanostructures opens up an exciting new field in the functionalization of nanomaterials. However, a better understanding of the interaction between graphene derivatives and inorganic precursors remains a challenge. This work provides an efficient strategy for exploring this interaction by first modifying graphene oxide with aniline, glycine, and glycyl glycine, respectively, and thus engineering the chemical microenvironments on graphene sheets for anchoring metal ions. After that, the affinities of graphene derivatives to various metal ions can be investigated with the help of a conventional electrochemical method. The method highlights the importance of graphene chemistry in hybrid preparation and provides design principles for chemical modifiers used in the construction of multifunctional carbon-inorganic nanostructures., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An acid-assisted ultrarapid thermal strategy is developed for constructing specifically functionalized graphene. The electrochemical performance of functionalized graphene can be boosted via elaborate coupling between the pseudocapacitance and the electronic double layer capacitance through rationally tailoring the structure of graphene sheets. This presents an opportunity for developing further high-performance graphene-based electrodes to bridge the performance gap between traditional capacitors and batteries., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Novel graphene-confined tin nanosheets (G/Sn/G) are constructed using an elaborately designed glucose-assisted chemical protocol. The as-synthesized G/Sn/G are featured with significantly enhanced lithium storage properties when compared with other graphene-based 0D/2D composite nanostructures, disclosing the merits of the 2D/2D composite featured with a surface-to-surface integration formula between graphene and the second 2D phase., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel strategy is developed for the large-scale fabrication of reduced graphene oxide films directly on flexible substrates in a controlled manner by the combination of a rod-coating technique and room-temperature reduction of graphene oxide. The as-prepared films display excellent uniformity, good transparency and conductivity, and great flexibility in a touch screen., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A green, facile, one-pot synthesis of well-defined Au NPs@POM-GNSs tricomponent nanohybrids is reported (POM stands for polyoxometalate and GNSs for graphene nanosheets). The synthesis is convenient, rapid and environmentally friendly. The POMs serve as both reducing, encapsulating molecules, and bridging molecules; this avoids the introduction of other organic toxic molecules. Characterization using transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy analysis is performed, and the structure of the prepared nanohybrids of Au NPs@POM-GNSs is verified. Most importantly, the amperometric measurements show the Au NPs@POM-GNSs nanohybrids have high catalytic activity with good sensitivity, good long-term stability, wide linear range, low detection limit, and fast response towards H(2)O(2) detection for application as an enzyme-free biosensor. Transformation of the POMs during H(2)O(2) detection does not affect the catalytic activities of the nanohybrids. Thus, the synergistic effect of Au NPs and GNSs in the nanohybrids leads to the enhanced catalytic property., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel, green, and highly efficient strategy for room-temperature reduction of solid-state graphene oxide films has been successfully developed using hydrogen-involved reduction with the assistance of a small amount of Pd catalyst. Based on this approach, flexible reduced graphene oxide films with high conductivity can be achieved and a roll-to-roll technique is expected., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tin-core/carbon-sheath coaxial nanocables directly integrated into a reduced graphene oxide (RGO) surface are constructed by a new strategy involving a RGO-mediated procedure. The as-synthesized nanocables, with uniform diameter and high aspect ratio, are versatile and exhibit excellent lithium storage properties, as revealed by electrochemical evaluation., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A 'gold rush' has been triggered all over the world for exploiting the possible applications of graphene-based nanomaterials. For this purpose, two important problems have to be solved; one is the preparation of graphene-based nanomaterials with well-defined structures, and the other is the controllable fabrication of these materials into functional devices. This review gives a brief overview of the recent research concerning chemical and thermal approaches toward the production of well-defined graphene-based nanomaterials and their applications in energy-related areas, including solar cells, lithium ion secondary batteries, supercapacitors, and catalysis., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The transmission of light through a metallic film stack on a transparent substrate, perforated with a periodic array of cylindrical holes/nanocavities, is studied. The structure is fabricated by using self-assembled nanosphere lithography. Since one layer in the film stack is made of a ferromagnetic metal (iron), exposure of the structure to a solution containing iron oxide nanoparticles causes nanoparticle accumulation inside the nanocavities. This changes the dielectric constant inside the nanocavities and thus affects the light transmission. Simulations are in good agreement with experiment, and show large sensitivity of the response to the amount of iron oxide nanoparticles deposited. This could be used in various sensor applications., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)