Quantum Spin Exchange Interactions to Accelerate the Redox Kinetics in Li-S Batteries.

Spin-engineering with electrocatalysts have been exploited to suppress the "shuttle effect" in Li-S batteries. Spin selection, spin-dependent electron mobility and spin potentials in activation barriers can be optimized as quantum spin exchange interactions leading to a significant reduction of the electronic repulsions in the orbitals of catalysts. Herein, we anchor the MgPc molecules on fluorinated carbon nanotubes (MgPc@FCNT), which exhibits the single active Mg sites with axial displacement. According to the density functional theory calculations, the electronic spin polarization in MgPc@FCNT not only increases the adsorption energy toward LiPSs intermediates but also facilitates the tunneling process of electron in Li-S batteries. As a result, the MgPc@FCNT provides an initial capacity of 6.1 mAh cm-2 even when the high sulfur loading is 4.5 mg cm-2, and still maintains 5.1 mAh cm-2 after 100 cycles. This work provides a new perspective to extend the main group single-atom catalysts enabling high-performance Li-S batteries.

Evolution of Stabilized 1T-MoS2 by Atomic-Interface Engineering of 2H-MoS2 /Fe-Nx towards Enhanced Sodium Ion Storage.

Metallic conductive 1T phase molybdenum sulfide (MoS2 ) has been identified as promising anode for sodium ion (Na+ ) batteries, but its metastable feature makes it difficult to obtain and its restacking during the charge/discharge processing result in part capacity reversibility. Herein, a synergetic effect of atomic-interface engineering is employed for constructing 2H-MoS2 layers assembled on single atomically dispersed Fe-N-C (SA Fe-N-C) anode material that boosts its reversible capacity. The work-function-driven-electron transfer occurs from SA Fe-N-C to 2H-MoS2 via the Fe-S bonds, which enhances the adsorption of Na+ by 2H-MoS2 , and lays the foundation for the sodiation process. A phase transfer from 2H to 1T/2H MoS2 with the ferromagnetic spin-polarization of SA Fe-N-C occurs during the sodiation/desodiation process, which significantly enhances the Na+ storage kinetics, and thus the 1T/2H MoS2 /SA Fe-N-C display a high electronic conductivity and a fast Na+ diffusion rate.

Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation.

Understanding the relationship between the electronic state of active sites and N2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well-defined FeN4 and MoN4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN4 on NRR behavior. The neighboring MoN4 can regulate the spin state of Fe center in FeN4 from high-spin (dxy 2 dyz 1 dxz 1 d z 2 1 d x 2 - y 2 1 ) to medium-spin (dxy 2 dyz 2 dxz 1 d z 2 1 ), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN4 instead of MoN4 , and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N2 . As a result, FeMoPPc with medium-spin FeN4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH3 yields for NRR than FePPc with high-spin FeN4 and MoPPc with MoN4 , respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers.

Regulating Fe-spin state by atomically dispersed Mn-N in Fe-N-C catalysts with high oxygen reduction activity.

As low-cost electrocatalysts for oxygen reduction reaction applied to fuel cells and metal-air batteries, atomic-dispersed transition metal-nitrogen-carbon materials are emerging, but the genuine mechanism thereof is still arguable. Herein, by rational design and synthesis of dual-metal atomically dispersed Fe,Mn/N-C catalyst as model object, we unravel that the O2 reduction preferentially takes place on FeIII in the FeN4 /C system with intermediate spin state which possesses one eg electron (t2g4eg1) readily penetrating the antibonding π-orbital of oxygen. Both magnetic measurements and theoretical calculation reveal that the adjacent atomically dispersed Mn-N moieties can effectively activate the FeIII sites by both spin-state transition and electronic modulation, rendering the excellent ORR performances of Fe,Mn/N-C in both alkaline and acidic media (halfwave positionals are 0.928 V in 0.1 M KOH, and 0.804 V in 0.1 M HClO4), and good durability, which outperforms and has almost the same activity of commercial Pt/C, respectively. In addition, it presents a superior power density of 160.8 mW cm-2 and long-term durability in reversible zinc-air batteries. The work brings new insight into the oxygen reduction reaction process on the metal-nitrogen-carbon active sites, undoubtedly leading the exploration towards high effective low-cost non-precious catalysts.

Synergistic Effect of Salinized Quinone for Entrapment of Polysulfides for High-Performance Li-S Batteries.

Lithium-sulfur (Li-S) batteries have attracted considerable attention in the energy storage field due to their high theoretical energy density and low price. However, the dissolution of polysulfides and the "shuttle effect" lead to serious capacity degradation, which greatly hinders the industrial application of Li-S batteries. Herein, we propose a bifunctional quinone-type salt to anchor polysulfides and suppress their dissolution for use in high-performance Li-S batteries. We find that the tetrahydroxy-1,4-benzoquinone disodium salt dimer (TBS-dimer) does not dissolve in organic electrolytes and can be generated at 400 °C. The abundant reactive keto groups and double bonds result in the TBS-dimers having numerous "hot spots" for capturing sulfur (TBS/S-400) in the three-dimensional space of the molecule. The insolubility and abundant active sites of the organic salt remarkably suppress the dissolution of lithium polysulfides. As a result, the TBS/S-400 composite delivers a capacity decay rate of only 0.023% per cycle over 600 cycles at 2 C. The use of organic salts to effectively suppress the dissolution of lithium polysulfides opens a new avenue for the practical applications of high-performance Li-S batteries.

Bubble-assisted fabrication of hollow CoMoO4 spheres for energy storage.

Herein, gas bubbles generated in situ from precursors assist the rapid construction of hollow sycamore fruit-like CoMoO4 spheres (HSCSs). This bubble-assisted fabrication strategy is easy to operate, ultra-fast, low cost and post-treatment-free, showing great potential for the large-scale production of HSCSs. The growth mechanism of HSCSs is discussed to reveal the evolution process, which may be generalized to the construction of a series of hollow ternary Mo-based oxides. The obtained HSCSs exhibit a superior specific capacitance and outstanding cyclic stability when applied in supercapacitors.

Effective NaBH4-exfoliated ultrathin multilayer Co(OH)2 nanosheets arrays and sulfidation for energy storage.

Facile engineering ultrathin nano structural materials is still a huge challenge for material science. Thereinto, the strategy of exfoliating shows great advantages. In this work, we develop a convenient approach to exfoliate Co(OH)2 nanosheets into ultrathin Co(OH)2 nanoflakes through NaBH4-exfoliation method. Moreover, the microstructures of the Co(OH)2 nanosheets are conveniently controlled by varying the exfoliation time. As a result, the obtained ultrathin Co(OH)2-72 h nanosheets deliver the excellent electrochemical performance. In order to improve the energy storage properties, the obtained ultrathin Co(OH)2 nanosheets are further modified to enhance the conductivity via sulfidation. Consequently, the synthesized Co(OH)2-72 h/CoS2 composites exhibit a specific capacitance of 2536 F g-1 at 1 A g-1, which is more outstanding than that of Co(OH)2-72 h. What's more, the Co(OH)2-72 h/CoS2 composites show a capacitance retention of 83.3% after 10 000 cycles. Besides, the assembled asymmetric supercapacitor displays a power density of 482 W kg-1 at an energy density of 36 Wh kg-1, demonstrating a large potential for application.

Designing 3D interconnected continuous nanoporous Co/CoO core-shell nanostructure electrodes for a high-performance pseudocapacitor.

A high-performance supercapacitor electrode is designed and fabricated with the 3D interconnected continuous nanoporous Co/CoO core-shell hybrid nanostructure grown on nickel foam. The Co/CoO core-shell hybrid nanostructures are obtained via a hydrothermal method, followed by high-temperature annealing in hydrogen atmosphere, and finally placed in air at 50 °C for 1 h. The Co/CoO core-shell nanostructure assembled by a conductive metal-core and a CoO shell, brings low resistance, high specific capacitance of 5.632 F cm-2 and good capability stability (81.5% capacitance retention after 6000 cycles). An asymmetric supercapacitor device built by the Co/CoO (positive electrode) and activated carbon (negative electrode) can deliver a working voltage of 1.7 V and display a high energy density of 0.002 67 Wh cm-2 at a power density of 0.001 62 W cm-2, which is far superior to that of a supercapacitor at a similar power density.

Asymmetric Supercapacitor Based on Porous N-doped Carbon Derived from Pomelo Peel and NiO Arrays.

A three dimensional (3D) porous framework-like N-doped carbon (PFNC) with a high specific surface area was successfully fabricated through ammonia doping and graphitization based on pomelo peel. The obtained PFNC exhibits an enhanced specific capacitance (260 F g(-1) at 1 A g(-1)) and superior cycling performance (capacitance retention of 84.2% after 10000 cycles at 10 A g(-1)) on account of numerous voids and pores which supply sufficient pathways for ion diffusion during cycling. Furthermore, a fabricated asymmetric PFNC//PFN device based on PFNC and porous flake-like NiO (PFN) arrays achieves a specific capacitance of 88.8 F g(-1) at 0.4 A g(-1) and an energy density of 27.75 Wh kg(-1) at a power density of 300 W kg(-1) and still retains 44 F g(-1) at 10 A g(-1) and 13.75 Wh kg(-1) at power density of 7500 W kg(-1). It is important that the device is able to supply two light-emitting diodes for 25 min, which demonstrates great application potential.

A "turn-off" SERS assay of heparin with high selectivity based on heparin-peptide complex and Raman labelled gold nanoparticles.

Stable SERS response originating from gold nanoparticles (Au NPs) is demonstrated for the first time to be suitable for detection of heparin with high selectivity. Herein we report a novel "turn-off" SERS assay for heparin based on Raman labelled Au NPs and competitive bonding between heparin and two specialized peptides, such as RKGSGRRLVKC (11-peptide) and CALNN (5-peptide). By means of coordination interactions and other non-electrostatic forces, these 5-peptide capped Au NPs are induced to undergo controllable aggregation upon the additive of 11-peptide and heparin with a concentration range (0-2.4 U/mL), which correspondingly cause quantitative changes of SERS intensity of 4-MBA conjugated on Au NPs. The decreased Raman intensity obtained by subtracting two cases of additives which contain only 11-peptide and the mixture of 11-peptide and heparin, is proportional to the concentration of heparin over a range of 0.2-2.4 U/mL (R(2)=0.99157), with a limit of detection (LOD) of 0.042 U/mL (S/N=3:1). Moreover, the proposed highly selective method has potential application for rapid, separation-free detection of heparin in human blood serum samples.

Controlling carbon encapsulation of gold nano-aggregates as highly sensitive and spectrally stable SERS tags for live cell imaging.

We describe a highly sensitive and spectrally stable surface-enhanced Raman scattering (SERS) tag for live cell imaging based on carbon-encapsulated gold nano-aggregates (CEGNAs). Our findings reveal that controlling the synthesis of the gold nano-aggregate core can be achieved under the mediation of cetyltrimethylammonium bromide (CTAB) through electrostatic forces and hydrophobic interactions, and as the number of particles in the aggregates increase, the relative SERS activity also increases hugely.