NiO nanobelts with exposed {110} crystal planes as an efficient electrocatalyst for the oxygen evolution reaction.

The electrocatalytic oxygen evolution reaction (OER) is necessary and challenging for converting renewable electricity into clean fuels, because of its complex proton coupled multielectron transfer process. Herein, we investigated the crystal plane effects of NiO on the electrocatalytic OER activity through combining experimental studies and theoretical calculations. The experimental results reveal that NiO nanobelts with exposed {110} crystal planes show much higher OER activity than NiO nanoplates with exposed {111} planes. The efficient OER activity of the {110} crystal planes comes from their intrinsically high catalytic ability and fast charge transfer kinetics. Density functional theory (DFT) shows that the {110} crystal planes possess a lower theoretical overpotential value for the OER, leading to a high electrocatalytic performance. This research broadens our vision to design efficient OER electrocatalysts by the selective exposure of specific crystal planes.

Interlayer Modification of Pseudocapacitive Vanadium Oxide and Zn(H2 O)n 2+ Migration Regulation for Ultrahigh Rate and Durable Aqueous Zinc-Ion Batteries.

The interlayer modification and the intercalation pseudocapacitance have been combined in vanadium oxide electrode for aqueous zinc-ion batteries. Intercalation pseudocapacitive hydrated vanadium oxide Mn1.4 V10 O24 ·12H2 O with defective crystal structure, interlayer water, and large interlayer distance has been prepared by a spontaneous chemical synthesis method. The inserted Mn2+ forms coordination bonds with the oxygen of the host material and strengthens the interaction between the layers, preventing damage to the structure. Combined with the experimental data and DFT calculation, it is found that Mn2+ refines the structure stability, adjusts the electronic structure, and improves the conductivity of hydrated vanadium oxide. Also, Mn2+ changes the migration path of Zn2+ , reduces the migration barrier, and improves the rate performance. Therefore, Mn2+ -inserted hydrated vanadium oxide electrode delivers a high specific capacity of 456 mAh g-1 at 0.2 A g-1 , 173 mAh g-1 at 40 A g-1 , and a capacity retention of 80% over 5000 cycles at 10 A g-1 . Furthermore, based on the calculated zinc ion mobility coefficient and Zn(H2 O)n 2+ diffusion energy barrier, the possible migration behavior of Zn(H2 O)n 2+ in vanadium oxide electrode has also been speculated, which will provide a new reference for understanding the migration behavior of hydrated zinc-ion.

Rational Design of Ion Transport Paths at the Interface of Metal-Organic Framework Modified Solid Electrolyte.

Solid-state lithium batteries have attracted great attention owing to their potential advantages in safety and energy density. Among various solid electrolytes, solid polymer electrolyte is promising due to its good viscoelasticity, lightweight, and low-cost processing. However, key issues of solid polymer electrolyte include poor ionic conductivity and low Li+ transference number, which limit its practical application. Herein, a new-type of ultraviolet cross-linked composite solid electrolyte (C-CSE), composed of ZIF-based ionic conductor (named ZIL) and polymer, is designed with enhanced ion transport. The ZIL is composed of ZIF-8 and ionic liquid, which can provide C-CSE with fast ion transport paths. Moreover, the proper pore size of ZIF-8 can restrict the migration of embedded ionic liquid and thus construct a solid-liquid transport interface between polymer chains and ZIF-8, which could achieve fast ion transport. In addition, ultraviolet irradiation can decrease the crystallization of C-CSE and thus increase the amorphous region. Consequently, the C-CSE show excellent electrochemical performance including high ionic conductivity of 0.426 mS cm-1 at 30 °C, high Li+ transference number of 0.67, and good Li|Li compatibility cycle over 1040 h. Experimental and computational results indicate that diffusion energy barrier of Li+ through ZIF-8 is smaller than that of polymer chains, which reveals a new Li+ transport mechanism between polymer chains and ZIL, from "chain-chain-chain" to "chain-ZIL-chain". This work demonstrates rational design of ion transport paths at the interface of solid electrolyte could facilitate the development of solid-state lithium batteries as a promising novel strategy.

Improved charge injection of edge aligned MoS2/MoO2 hybrid nanosheets for highly robust and efficient electrocatalysis of H2 production.

Molybdenum disulfide (MoS2) can be an efficient electro-catalyst for the hydrogen evolution reaction (HER) as an alternative to precious metals, but significant efforts are still needed to further improve its efficiency. Among various approaches, the formation of edge aligned MoS2 on an electrically conductive support is highly promising for cost-effective H2 production. Nevertheless, catalysis is highly impeded by the poor charge transport between the electrode materials and also between the multilayers of MoS2. This research presents a strategy to improve the HER catalysis by binding layers of metallic molybdenum dioxide (MoO2) and MoS2 to form hybrid MoS2/MoO2 nanosheets (attached and cross-linked to each other). Taking advantage of the hybrid structure and the mechanical strength of the carbon cloth, a catalyst with outstanding catalytic performance in the HER is demonstrated. This work shows not only a strategy to efficiently improve the electrochemical process, but also the preparation of a highly efficient catalyst for constant and robust H2 production.

One-Step Synthesis of a Nanosized Cubic Li2TiO3-Coated Br, C, and N Co-Doped Li4Ti5O12 Anode Material for Stable High-Rate Lithium-Ion Batteries.

Nanosized Li4Ti5O12 with both a Li2TiO3 coating and C-N-Br co-doping (CLLTO) was successfully synthesized via a facile reverse microemulsion method in one step using hexadecyl trimethyl ammonium bromide as a surface control agent and as a carbon, nitrogen, and bromine source. A uniform Li2TiO3 layer was formed on the surface and strongly adhered to the host material Li4Ti5O12 (LTO), which played an important role in improving the cyclic stability of CLLTO. The thin and stable Li2TiO3 layer has the same cubic structure as LTO, which provides many three-dimensional channels for ion transport. C, N, and Br co-doping in CLLTO promoted the transition of Ti4+ to Ti3+ in Li4Ti5O12, which could improve the capacity and facilitate the Li+ ion and electron transfer at the interface. The conductive behavior induced by co-doping was estimated by UV-vis diffuse reflectance spectra and further supported by theoretical calculations. The electrical conductivity of both p-type and n-type LTO can be well improved by co-doping C, N, and Br. This improvement may be due to the band gap reduction and the increased n-type electronic modification of the entire LTO. Owing to the synergistic effect of coating, co-doping, and nanosizing at one time, the CLLTO exhibits a high discharge capacity of 177.3-153.9 mA h g-1 at the working rate of 0.1C-20C, with a capacity retention of 86%. The stable cycling of CLLTO is also obtained after 500 cycles at 20C, with a capacity retention of 95.5% (approximately 8 times higher than that of pure LTO) and almost 100% Coulombic efficiency. With high capacity, excellent rate performance, and good cycling stability, CLLTO can be applied in high-power lithium-ion batteries.

Opening Magnesium Storage Capability of Two-Dimensional MXene by Intercalation of Cationic Surfactant.

Two-dimensional (2D) Ti3C2 MXene has attracted great attention in electrochemical energy storage devices (supercapacitors and lithium-ion and sodium-ion batteries) due to its excellent electrical conductivity as well as high volumetric capacity. Nevertheless, a previous study showed that multivalent Mg2+ ions cannot reversibly insert into MXene, resulting in a negligible capacity. Here, we demonstrate a simple strategy to achieve high magnesium storage capability for Ti3C2 MXene by preintercalating a cationic surfactant, cetyltrimethylammonium bromide (CTAB). Density functional theory simulations verify that intercalated CTA+ cations reduce the diffusion barrier of Mg2+ on the MXene surface, resulting in the significant improvement of the reversible insertion/deinsertion of Mg2+ ions between MXene layers. Consequently, the MXene electrode exhibits a desirable volumetric specific capacity of 300 mAh cm-3 at 50 mA g-1 as well as outstanding rate performance. This work endows MXene material with an application in electrochemical energy storage and, simultaneously, introduces magnesium battery materials as a member.

Tuning the Doping Types in Graphene Sheets by N Monoelement.

The doping types of graphene sheets are generally tuned by different dopants with either three or five valence electrons. As a five-valence-electrons element, however, nitrogen dopants in graphene sheets have several substitutional geometries. So far, their distinct effects on electronic properties predicted by theoretical calculations have not been well identified. Here, we demonstrate that the doping types of graphene can be tuned by N monoelement under proper growth conditions using chemical vapor deposition (CVD), characterized by combining scanning tunneling microscopy/spectroscopy, X-ray/ultraviolet photoelectron spectroscopy, Hall effect measurement, Raman spectroscopy, and density functional theory calculations. We find that a relatively low partial pressure of CH4 (mixing with NH3) can lead to the growth of dominant pyridinic N substitutions in graphene, in contrast with the growth of dominant graphitic N substitutions under a higher partial pressure of CH4. Our results unambiguously confirm that the pyridinic N leads to the p-type doping, and the graphitic N leads to the n-type doping. Interestingly, we also find that the pyridinic N and the graphitic N are preferentially separated in different domains. Our findings shed light on continuously tuning the doping level of graphene monolayers by using N monoelement, which can be very convenient for growth of functional structures in graphene sheets.

Curvature-dependent adsorption of water inside and outside armchair carbon nanotubes.

The curvature dependence of the physisorption properties of a water molecule inside and outside an armchair carbon nanotube (CNT) is investigated by an incremental density-fitting local coupled cluster treatment with single and double excitations and perturbative triples (DF-LCCSD(T)) study. Our results show that a water molecule outside and inside (n, n) CNTs (n = 4, 5, 6, 7, 8, 10) is stabilized by electron correlation. The adsorption energy of water inside CNTs decreases quickly with the decrease of curvature (increase of radius) and the configuration with the oxygen pointing toward the CNT wall is the most stable one. However, when the water molecule is adsorbed outside the CNT, the adsorption energy varies only slightly with the curvature and the configuration with hydrogens pointing toward the CNT wall is the most stable one. We also use the DF-LCCSD(T) results to parameterize Lennard-Jones (LJ) force fields for the interaction of water both with the inner and outer sides of CNTs and with graphene representing the zero curvature limit. It is not possible to reproduce all DF-LCCSD(T) results for water inside and outside CNTs of different curvature by a single set of LJ parameters, but two sets have to be used instead. Each of the two resulting sets can reproduce three out of four minima of the effective potential curves reasonably well. These LJ models are then used to calculate the water adsorption energies of larger CNTs, approaching the graphene limit, thus bridging the gap between CNTs of increasing radius and flat graphene sheets.

Iron-phthalocyanine molecular junction with high spin filter efficiency and negative differential resistance.

We investigate the spin transport properties of iron-phthalocyanine (FePc) molecule sandwiched between two N-doped graphene nanoribbons (GNRs) based on the density functional theory and nonequilibrium Green's function methods. Our calculated results clearly reveal that the FePc molecular junction has high spin-filter efficiency as well as negative differential resistance (NDR). The zero-bias conductance through FePc molecule is dominated by the spin-down electrons, and the observed NDR originates from the bias-dependent effective coupling between the FePc molecular orbitals and the narrow density of states of electrodes. The remarkable high spin-filter efficiency and NDR are robust regardless of the edge shape and the width of GNRs, and the N-doping site in GNRs. These predictions indicate that FePc junction holds great promise in molecular electronics and spintronics applications.