Triboelectric Nanogenerators Assembled by Cobalt(II) Coordination Polymer Incorporated Composite Films and their Application for Self-Powered Anticorrosion.

A friction layer with stability and durability is important to promote the practical application of triboelectric nanogenerators (TENGs). In this work, a two-dimensional cobalt coordination polymer (Co-CP) was successfully synthesized using cobalt nitrate, 4,4',4''-tricarboxyltriphenylamine and 2,2'-bipyridine. To clearly clarify the effect of the doping proportions of Co-CP and the types of composite polymers on the output performance of the TENG, Co-CP was combined with two organic polymers having different polarities (polyvinylidene fluoride (PVDF) and ethyl cellulose (EC)) to form a series of composite films, which were used as the friction electrode materials to fabricate TENGs. Electrical characterizations indicated that a high output current and voltage were obtained from the TENG based on 15 wt.% Co-CP incorporated in PVDF (Co-CP@PVDF), which could be further improved by the Co-CP@EC composite film at the same doping ratio. Furthermore, the optimally fabricated TENG was demonstrated to prevent electrochemical corrosion of carbon steel.

Fabrication of Nitrogen-Doped Carbon-Coated NiS1.97 Quantum Dots for Advanced Magnesium-Ion Batteries.

Magnesium (Mg) batteries have garnered considerable interest because of their safety characteristics and low costs. However, the practical application of Mg batteries is hindered by the slow diffusion of Mg ions in the cathode materials. In this study, we prepared NiS1.97 quantum dot composites with nitrogen doping and carbon coating (NiS1.97 QDs@NC) using a one-step sulfurization process with NiO QDs/Ni@NC as the precursor. We applied the prepared NiS1.97 QDs/Ni@NC-based cathodes to Mg batteries because of the large surface area of the quantum dot composite, which provided abundant intercalation sites. This design ensured efficient deintercalation of magnesium ions during charge-discharge processes. The fabricated NiS1.97 QDs@NC displayed a high reversible Mg storage capacity of 259.1 mAh g-1 at 100 mA g-1 and a good rate performance of 96.0 mAh g-1 at 1000 mA g-1. Quantum dot composites with large surface areas provide numerous embedded sites, which ensure effective deintercalation of Mg ions during cycling. Thus, the proposed cathode synthesis strategy is promising for Mg-ion-based energy storage systems.

Distributed Li-Ion Flux Enabled by Sulfonated Covalent Organic Frameworks for High-Performance Lithium Metal Anodes.

Metallic Li is considered the most promising anode material for high-energy-density batteries owing to its high theoretical capacity and low electrochemical potential. However, inhomogeneous lithium deposition and uncontrollable growth of lithium dendrites result in low lithium utilization, rapid capacity fading, and poor cycling performance. Herein, two sulfonated covalent organic frameworks (COFs) with different sulfonated group contents are synthesized as the multifunctional interlayers in lithium metal batteries. The sulfonic acid groups in the pore channels can serve as Li-anchoring sites that effectively coordinate Li ions. These periodically arranged subunits significantly guide uniform Li-ion flux distribution, guarantee smooth Li deposition, and reduce lithium dendrite formation. Consequently, these characteristics afford an excellent quasi-solid-state electrolyte with a high ionic conductivity of 1.9 × 10-3  S  cm-1 at room temperature and a superior Li++ transference number of 0.91. A Li/LiFePO4 battery with the COF-based electrolyte exhibited dendrite-free Li deposition during the charge process, accompanied by no capacity decay after 100 cycles at 0.1 C.

Rationally Designed Three-Layered TiO2 @amorphous MoS3 @Carbon Hierarchical Microspheres for Efficient Potassium Storage.

Amorphous MoS3 has been an attractive electrode material for sodium-ion batteries and lithium-sulfur batteries. However, the potassium storage capability of amorphous MoS3 remains unreported. Herein, the construction of hybrid hierarchical microspheres composed of amorphous MoS3 nanosheets dual-confined with TiO2 core, and nitrogen-doped carbon shell layer (denoted as TiO2 @A-MoS3 @NC) via a self-templating method, combined with a low-temperature sulfurization process as a new anode material for potassium-ion batteries (PIBs), is reported. Benefitting from the unique structural merits including unique 1D chain structure, disordered arrangement of atoms and a large number of defects of amorphous MoS3 , more active heterointerfacial sites, effectively mitigated volume change, good electrical contact, and easy K+ ion migration, the TiO2 @A-MoS3 @NC microspheres exhibit excellent potassium-storage performance with high specific capacity, superior rate capability, and cycling stability.

Design of Photoactive Covalent Organic Frameworks as Heterogeneous Catalyst for Preparation of Thiophosphinates from Phosphine Oxides and Thiols.

Two new covalent organic frameworks (COFs) were synthesized from 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl)tetraaniline and 2,5-dimethoxyterephthalaldehyde (Py-DMTA-COF) or 2',5'-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde (Py-DMTPDA-COF) under solvothermal conditions. These two COFs were further facilely developed as efficient photocatalytic platforms for the synthesis of thiophosphinates. Py-DMTA-COF exhibited better photocatalytic activity, broad substrate applicability, and excellent recycling capacity for the preparation of thiophosphinates from P(O)H compounds and thiols compared to Py-DMTPDA-COF. This methodology was further extended to the seamless gram-scale production of target phosphorothioate derivatives. The results demonstrate that COFs can provide a robust platform for developing metal-free, base-free, highly efficient, and reusable heterogeneous photocatalysts for organic transformations.

Output Enhancement of Triboelectric Nanogenerators Based on Hierarchically Regular Cadmium Coordination Polymers for Photocycloaddition.

Exploiting the well-arranged and tunable frameworks of crystalline materials, we herein report coordination polymers (CPs) with modulated hierarchical structures as triboelectric materials to construct and extend the application scope of triboelectric nanogenerators (TENGs). Different lengths and shapes of bridging ligands [4,4'-bpa = 1,2-bis(4-pyridyl)ethane, 4,4'-bpe = 1,2-bis(4-pyridyl)ethene, and 4,4'-bpp = 1,3-di(2-pyridyl)propane for 1, 2, and 3, respectively] were used to construct Cd-CP-based hierarchical frameworks. These compounds were used as triboelectric materials, and their electronic structure contributions were determined by the output of the corresponding TENGs. The results indicated that 2-TENG with the 4,4'-bpe ligand had the highest output, attributed to the improvement in the electron activity due to the π-conjugation group in the bridging ligand, which was further verified by density functional theory calculations. Furthermore, 2@PVDF (PVDF = polyvinylidene fluoride) composite films with different concentrations of Cd-CP were prepared. Detailed electrical characterizations revealed that the arrangement of 12% active constituents of Cd-CP-2 effectively enhanced the output performance of 2@PVDF-TENG, which could light up an ultraviolet lamp plate to successfully execute the [2 + 2] photocycloaddition.

Metal-Ion Coupling in Metal-Organic Framework Materials Regulating the Output Performance of a Triboelectric Nanogenerator.

Metal-organic frameworks (MOFs) as friction nanopower generation materials have attracted more and more research and attention because of the inherent three-dimensional framework structure and large aperture. In this work, the ZUT-75(Mn) with a one-dimensional pore structure was synthesized by using electron-rich benzimidazole carboxylic acid ligands, and isomorphic offspring MOF materials were obtained by single crystal-single crystal solvent-assisted metal-ion exchange. The exchange process was monitored by liquid UV-vis spectroscopy, atomic absorption spectrometry, and energy-dispersive X-ray spectroscopy. The metal-oxygen coordination energy, X-ray photoelectron spectroscopy binding energy, and hard-soft acid-base principle verified the spontaneity of the central-metal-exchange reaction. The four materials were applied to a triboelectric nanogenerator (TENG), and the output performance law of ZUT-75 was Co-MT > Zn-MT > Cu-MT > Mn-MT. Among them, the charge and power densities of Co-MT were up to 127.05 µC m-2 and 3280.50 mW m-2. When the density functional theory calculation and variable-temperature magnetic susceptibility test results were combined, it was concluded that low metal-ion-coupling degree promoted the formation and transfer of contact electrifications, which greatly improved the output performance of the TENG. This work provided a new idea for improving the output performance of the TENG.

Accumulation of Sulfonic Acid Groups Anchored in Covalent Organic Frameworks as an Intrinsic Proton-Conducting Electrolyte.

Covalent organic frameworks (COFs) are a novel class of crystalline porous polymers, which possess high porosity, excellent stability, and regular nanochannels. 2D COFs provide a 1D nanochannel to form the proton transport channels. The abovementioned features afford a powerful potential platform for designing materials as proton transportation carriers. Herein, the authors incorporate sulfonic acid groups on the pore walls as proton sources for enhancing proton transport conductivity in the 1D channel. Interestingly, the sulfonic acid COFs (S-COFs) electrolytes being binder free exhibit excellent proton conductivity of ≈1.5 × 10-2 S cm-1 at 25 ℃ and 95% relative humidity (RH), which rank the excellent performance in standard proton-conducting electrolytes. The S-COFs electrolytes keep the high proton conduction over the 24 h. The activation energy is estimated to be as low as 0.17 eV, which is much lower than most reported COFs. This research opens a new window to evolve great potential of structural design for COFs as the high proton-conducting electrolytes.

A Double-Helix Metal-Chain Metal-Organic Framework as a High-Output Triboelectric Nanogenerator Material for Self-Powered Anticorrosion.

The development of novel metal organic framework (MOF) friction power generation materials with high stability is important. This paper reports the first example of a double-helix metal chain organic framework with a network structure (ZUT-8). ZUT-8 shows high chemical stability, functional adjustability, and excellent output performance of friction power generation, which is superior to traditional coordination polymer materials. The cathodic protection system with ZUT-8 can prevent metal corrosion significantly. The output performance can be improved effectively by enhancing the conjugate effect of the linker. The theoretical calculation results showed that an increase in the degree of conjugation could significantly reduce the band gap, thereby affecting the friction power output signal. This study opens the door to constructing MOF materials with a double-helix metal chain and will promote their potential applications in self-powered electrochemical cathodic protection.

Covalent Organic Frameworks with Tailored Functionalities for Modulating Surface Potentials in Triboelectric Nanogenerators.

Designing materials with high triboelectric is an efficient way of improving output performance of triboelectric nanogenerators (TENGs). Herein, we synthesized a series of covalent organic frameworks (COFs) with similar skeletons but various functional groups ranging between electron-donating and electron-withdrawing. These COFs form an ideal platform for clarifying the contribution of each group to TENG performance because the pore wall is perturbed in a predesigned manner. Kelvin probe force microscopy and computational data suggest that surface potentials and electron affinities of COFs can be improved by introducing electron-donating or withdrawing groups, with the highest values observed for fluorinated COF. The TENG with fluorinated COF delivered an output voltage and current of 420 V and 64 µA, respectively, which are comparable to other reported materials. This strategy can be used to efficiently screen suitable frameworks as TENG materials with excellent output performance.

Recent Progress on the Alloy-Based Anode for Sodium-Ion Batteries and Potassium-Ion Batteries.

High-energy batteries with low cost are urgently needed in the field of large-scale energy storage, such as grid systems and renewable energy sources. Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) with alloy-based anodes provide huge potential due to their earth abundance, high capacity, and suitable working potential, and are recognized as attractive alternatives for next-generation batteries system. Although some important breakthroughs have been reported, more significant improvements are still required for long lifetime and high energy density. Herein, the latest progress for alloy-based anodes for SIBs and PIBs is summarized, mainly including Sn, Sb, Ge, Bi, Si, P, and their oxides, sulfides, selenides, and phosphides. Specifically, the material designs for the desired Na+ /K+ storage performance, phase transform, ionic/electronic transport kinetics, and specific chemical interactions are discussed. Typical structural features and research strategies of alloy-based anodes, which are used to facilitate processes in battery development for SIBs and PIBs, are also summarized. The perspective of future research of SIBs and PIBs is outlined.

Tunable and Nacre-Mimetic Multifunctional Electronic Skins for Highly Stretchable Contact-Noncontact Sensing.

Electronic skins (e-skins) have attracted great attention for their applications in disease diagnostics, soft robots, and human-machine interaction. The integration of high sensitivity, low detection limit, large stretchability, and multiple stimulus response capacity into a single e-skin remains an enormous challenge. Herein, inspired by the structure of nacre, an ultra-stretchable and multifunctional e-skin with tunable strain detection range based on nacre-mimetic multi-layered silver nanowires /reduced graphene oxide /thermoplastic polyurethane mats is fabricated. The e-skin possesses extraordinary strain response performance with a tunable detection range (50 to 200% strain), an ultralow response limit (0.1% strain), a high sensitivity (gauge factor up to 1902.5), a fast response time (20 ms), and an excellent stability (stretching/releasing test of 11 000 cycles). These excellent response behaviors enable the e-skin to accurately monitor full-range human body motions. Additionally, the e-skin can detect relative humidity quickly and sensitively through a reversible physical adsorption/desorption of water vapor, and the assembled e-skin array exhibits excellent performance in noncontact sensing. The tunable and multifunctional e-skins show promising applications in motion monitoring and contact-noncontact human machine interaction.

Programmable Triboelectric Nanogenerators Dependent on the Secondary Building Units in Cadmium Coordination Polymers.

Precisely controlling the coordination microenvironment and electronic features of polynuclear secondary building units (SBUs) in coordination polymers (CPs) is an efficient approach to governing their fundamental performance. Here, different multinuclear SBUs (binuclear, trinuclear, and pentanuclear SBUs for 1-3, respectively) were introduced into Cd-based CPs, which were used as frictional electrode materials, to clarify the contributions of polynuclear Cd-SBUs through the output of triboelectric nanogenerators (TENGs). The results demonstrated that 1-TENG with binuclear Cd-SBUs possessed the highest output, whereas 3-TENG with the pentanuclear Cd-SBUs indicated the minimum output, suggesting that the binuclear Cd-SBUs in 1 lost electrons most readily and generated much more charge, which was further confirmed by density functional theory calculations. This work opened a new prospect to confirm the gaining/losing capability of polynuclear Cd-SBUs in CPs and provided an effective approach to tuning both the stability and functionality of polynuclear CPs as frictional pair materials to regulate the output of CPs-based TENGs.

Organosulfonate Counteranions-A Trapped Coordination Polymer as a High-Output Triboelectric Nanogenerator Material for Self-Powered Anticorrosion.

Selection of the friction electrode materials is crucial to the performance of a triboelectric nanogenerator (TENG). In the present study, a metal-organic coordination complex containing organosulfonate counteranions with electron-donating ability was synthesized through the coordination-driven self-assembly approach under mild reaction conditions and was chosen as a positive electrode material to construct a triboelectric nanogenerator, exhibiting high-output performance with a peak value of short circuit current density of 98.6 µA and an output voltage of 1180 V. As a practical application, it was shown to light up 1488 commercial green LEDs and power an anticorrosion system device to protect metals from corrosion.

Bromine-Functionalized Covalent Organic Frameworks for Efficient Triboelectric Nanogenerator.

Covalent organic frameworks (COFs) enable precise integration of various organic building blocks into porous skeletons through topology predesign. Here, we report the first example of COFs by integrating electron withdrawing bromine group onto the skeletons for triboelectric nanogenerators (TENG). The resulting framework exhibits high surface area and good crystallinity. Thus, the bromine functionalized COF has more regular aligned π columns and arrays over the skeleton than bare COFs, which in turn significantly enhances charge transport ability. As a result, bromine functionalized COFs showed higher electrical output performance at 5 Hz with a peak value of short circuit current density of 43.6 µA and output voltage of 416 V, which is 2 and 1.3 times higher than those of bare COFs (21.6 µA and 318 V), respectively. These results demonstrated that this strategy for engineering electron withdrawing groups on the skeleton could open a new aspect of COFs for developing TENG devices.

Reversible Structural Transformations of Metal-Organic Frameworks as Artificial Switchable Catalysts for Dynamic Control of Selectively Cyanation Reaction.

The synthesis of molecular-level artificial switchable catalysts, of which activity in different chemical processes can be switched by controlling different stimuli, has provided a new paradigm to perform mechanical tasks and measurable work. In this work, to obtain highly effective and regioselective artificial switchable catalysts, a hierarchical anion-pillared framework {(H3 O)[Cu(CPCDC)(4,4'-bpy)]}n (1; H3 CPCDC=9-(4-carboxyphenyl)-9H-carbazole-3,6-dicarboxylic acid, 4,4'-bpy=4,4'-bipyridine), including free [H3 O]+ ions as guest molecules, was constructed. Upon dissolve-exchange-crystallization behavior, fascinating reversible structural transformations proceeded between anion framework 1 and neutral 2D stair-stepping framework {[Cu(CPCDC)(4,4'-bpe)]}n (2; 4,4'-bpe=4,4'-vinylenedipyridine). Moreover, frameworks 1 and 2 can act as heterogeneous artificial switchable catalysts to selectively promote the direct cyanation reaction of terminal alkynes and azobisisobutyronitrile. The results indicated that 1 and 2 exhibited excellent selectivity to generate vinyl isobutyronitrile skeletons or propiolonitrile frameworks, respectively, as unique products. Furthermore, indicating paper, GC-MS, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis demonstrated that the reversible structural transformations endowed 1 and 2 with well-defined platforms to stabilize the isobutyronitrile and CN sources through the different catalytic pathways.

Directed Structural Transformations of Coordination Polymers Supported Single-Site Cu(II) Catalysts To Control the Site Selectivity of C-H Halogenation.

A main difficulty in C-H bond functionalization is to undertake the catalyst control accurately where the reaction takes place. In this work, to achieve highly effective and regioselective single-site catalysts, a three-dimensional (3D) rhombus-like framework of {[Mn(Hidbt)DMF]·H2O}n (1) [H3idbt = 5,5'-(1H-imidazole-4,5-diyl)-bis(2H-tetrazole)] containing coordinated DMF molecules was constructed. For the dissolution-recrystallization structural transformation process, attractive structural transformations proceeded from 1 to a new crystalline species formulated as {[Mn3(idbt)2(H2O)2]·3H2O}n (2) with a 3D windowlike architecture, and then the Mn ions in 2 could be exchanged with Cu ions through cation exchange in a single-crystal to single-crystal fashion to produce the Cu-exchanged product {[Mn2Cu(idbt)2(H2O)2]·3H2O}n (2a), which had a windowlike framework like that of 2. Furthermore, 2 and 2a were used as heterogeneous catalysts for the regioselective C-H halogenation of phenols with N-halosuccinimides (NCS and NBS) to produce the site selective single monohalogenated products. It was found that the catalytic activity and site selectivity of 2a were much higher than those of 2, because the unique structural features of 2a with the uniformly dispersed CuII active centers served as a single-site catalyst with a site-isolated and well-defined platform to promote the C-H halogenation reaction in regiocontrol and guide an orientation that favored the para selectivity during the reaction process.

Syntheses, Structures, and Solution Studies of Multicomponent Macrocycles and Cages Based on Versatile Ligands.

Different types of multinuclear half-sandwich rhodium macrocycles and cages were designed and synthesized by using two similar multifunctional hydroxamate ligands (pyrazine-2-hydroxamic acid (NaHL1 ) and 4,4'-bipyridine-2-hydroxamic acid (KHL2 )) featuring one monodentate site and two pairs of chelating sites. The RhIII -PdII heterometallic macrocycles were constructed by using the semi-open palladium(II) source [Pd(en)Cl2 ] with two free acceptor sites. However, only one kind of macrocycle was found when the shorter ligand L1 was used, while in for the larger ligand, various spectroscopic techniques demonstrated the coexistence of hexanuclear and octanuclear macrocycles in solution and the proportions of both components depended on concentration and temperature. The palladium salt Pd(NO3 )2 , as a source of "naked" Pd2+ , was introduced to assemble the cuboid-shaped cage composed of two types of metal ions and three types of organic ligands. In addition, two silver(I)-containing mixed-metal complexes bridged by pyrazine were obtained, in which two forms of decanuclear complex with C2v and C2h point symmetry cocrystallized-one is a polymeric structure and the other is a discrete cage. However, the third form, with D2 point symmetry, was found in the larger cage.

Solvent-Induced Assembly of Sliver Coordination Polymers (CPs) as Cooperative Catalysts for Synthesizing of Cyclopentenone[b]pyrroles Frameworks.

A series of solvent-induced Ag-based coordination polymers (CPs) (1-3), which were synthesized by regulating the size, shape, and polarity of solvent molecules (EtOH, iPrOH, 1,4-dioxane) as structure-directing agents, has been used as heterogeneous catalysts to explore how the metal-metal bonds could serve as cooperative catalysis for tandem acylation-Nazarov cyclization reaction to prepare cyclopentenone[b]pyrroles frameworks. Structural conversions from a three-dimensional (3D) framework of 1 to the structure of 2 with Ag-Ag-Ag bonds and to the two-dimensional (2D) framework of 3 with Ag-Ag bonds, arising from the different sizes, shapes, and polarities of the solvent molecules, were observed. Futhermore, the effective cooperative catalysis for tandem acylation-Nazarov cyclization reaction has been evidenced by the significantly transformed connection modes of Ag-Ag interactions in 1-3. As a result, the unique structural characteristics of 2, especially containing the Ag-Ag-Ag bonds, endow 2 with intact multinuclear reaction pathways and well-defined multinuclear platforms that can execute tandem acylation-Nazarov cyclization reaction through the cooperative effect of Ag-Ag-Ag interactions during the catalytic process.

Innovative solvent-free compound-direct synthesis of defect-rich ultra-thin NiS nanosheets for high-performance supercapacitors.

Defect engineering in NiS nanosheets is an effective method to improve their surface properties and electronic structure for promoting electrochemical properties. However, a tunable, simple, and safe strategy for the introduction of abundant defect sites with a high activity into NiS with a special microstructure is worth developing. Herein, a novel hierarchical micro-flower-like NiS using graphene-like ultra-thin nanosheets with abundant defects as the building blocks was facilely synthesized by an innovative solvent-free compound-direct reaction strategy, which employed cost-efficient NaCl as the friction agent and dispersant to ensure adequate contact between sulfur ions and nickel ions and regulate the growth direction of NiS. Graphene-like ultra-thin NiS nanosheets effectively shorten the transport distance of ions and electrons. Defect engineering in NiS nanosheets provides more adsorption and storage sites for ions and high-activity sites for electrode materials, as well as adjusts the local electronic structure so as to effectively promote ion diffusion and charge transfer. The high performance of the as-obtained N-NiS electrode is illustrated by fabricating an asymmetric supercapacitor, which exhibits a specific capacitance of 351.5 F g-1 and energy density of 71.0 W h kg-1 at a power density of 229.3 W kg-1. The solvent-free compound-direct reaction strategy demonstrated in this study provides a new direction for the synthesis of high-performance nanomaterials for electrochemical energy storage applications.