Unprecedented 100% conversion from pyridinic to pyrrolic nitrogen configuration for electrochemically active nitrogen-doped carbon materials.

Nitrogen-doped carbons with promising electrochemical performance exhibit a strong dependence on nitrogen configuration. Therefore, accurate control of nitrogen configurations is crucial to clarify their influence. Unfortunately, there is still no well-defined conversion route to finely control nitrogen configuration. Herein, we proposed the concept of 100% conversion from pyridinic to pyrrolic nitrogen in carbon materials through low-temperature pyrolysis and alkali activation of hydroxypyridine-3-halophenol-formaldehyde resins. Their dehalogenation pyrolysis promotes formation of carbon intermediates and conversion of tautomeric pyridone and hydroxypyridine into pyrrolic and pyridinic nitrogen through eliminating carbonyl and hydroxyl functionalities, respectively. Continuous thermal alkali activation introduces hydroxyl groups into carbon materials, converting pyridinic species to intermediate hydroxypyridine and pyridone; subsequently, these configurations transform to pyridinic and pyrrolic nitrogen, respectively, and finally, an excessive alkali ensures 100% conversion from pyridinic to pyrrolic nitrogen. NaOH activation for pyrrolic and pyridinic nitrogen co-doped carbon and KOH activation for model nitrogen-containing compounds including acridine, phenanthridine, and acridone further confirm that alkali activation plays an indispensable role in 100% conversion from pyridinic to pyrrolic units through the tautomeric hydroxypyridine and pyridone intermediates. Low-temperature alkali-induced controllable conversion of nitrogen configuration in carbon materials is suitable modulating nitrogen configurations for almost all nitrogen-doped carbon materials in electrochemical applications.

In situ observation of the electrochemical lithiation of a single MnO@C nanorod electrode with core/shell structure.

Transition metal oxides (TMOs) play a crucial role in lithium-ion batteries (LIBs) due to their high theoretical capacity, natural abundance, and benign environmental impact, but they suffer from limitations such as cyclability and high-rate discharge ability. One leading cause is the lithiation-induced volume expansion (LIVE) for "conversion"-type TMOs, which can result in high stress, fracture and pulverization. Using carbon layers is an effective strategy to provide effective volumetric accommodation for lithium-ion (Li+) insertion; however, the detailed mechanism is unknown. In order to clarify the working mechanism of nanoscale LIBs, herein, the discharge reactions in a nanoscale LIB were investigated through in situ environmental transmission electron microscopy (ETEM). Visualization of the Li+ insertion process of MnO@C nanorods (NRs) with core/shell structure (CSS) and internal void space (IVS) was achieved. The LIVE occurred in a consecutive two-step mode, i.e., a LIVE of the carbon layer followed by a co-LIVE of the carbon layer and MnO. No volume contraction of the IVS was observed. The IVS acted as a buffer relieving the stress of the carbon layer. The carbon layer with IVS simultaneously improved the cyclability and the high-rate discharge ability of the electrode, pointing to a promising route for building better TMO electrode materials.

Turning on Zn 4s Electrons in a N2 -Zn-B2 Configuration to Stimulate Remarkable ORR Performance.

A zinc-based single-atom catalyst has been recently explored with distinguished stability, of which the fully occupied Zn2+ 3d10 electronic configuration is Fenton-reaction-inactive, but the catalytic activity is thus inferior. Herein, we report an approach to manipulate the s-band by constructing a B,N co-coordinated Zn-B/N-C catalyst. We confirm both experimentally and theoretically that the unique N2 -Zn-B2 configuration is crucial, in which Zn+ (3d10 4s1 ) can hold enough delocalized electrons to generate suitable binding strength for key reaction intermediates and promote the charge transfer between catalytic surface and ORR reactants. This exclusive effect is not found in the other transition-metal counterparts such as M-B/N-C (M=Mn, Fe, Co, Ni and Cu). Consequently, the as-obtained catalyst demonstrates impressive ORR activity, along with remarkable long-term stability in both alkaline and acid media. This work presents a new concept in the further design of electrocatalyst.

Highly efficient charge transfer in CdS-covalent organic framework nanocomposites for stable photocatalytic hydrogen evolution under visible light.

A facile and effective impregnation combined with photo-deposition approach was adopted to deposit cadmium sulfide (CdS) nanoparticles on CTF-1, a covalent triazine-based frameworks (CTFs). In this system, CTF-1 not only acted as supporter but also served as photocatalyst and electron donor. The performance of the obtained CdS deposited CTF-1 (CdS-CTF-1) nanocomposite was evaluated by H2 evolution reaction under visible light irradiation. As a result, CdS-CTF-1 exhibited high H2 production from water, far surpassing the CdS/CTF-1 nanocomposite, in which CdS was deposited via solvothermal method. The high activity of CdS-CTF-1 was attributed to the confined CdS nanoparticles with small size, leading to expose more active sites. In addition, time-resolved spectroscopy indicated that the superior performance of CdS-CTF-1 also can be ascribed to the fast electron transfer rate and injection efficiency (KET = 0.18 × 109 s-1, ηinj = 39.38%) between CdS and CTF-1 layers, which are 3.83 times faster and 4.84 times higher than that of CdS/CTF-1 nanocomposite. This work represents the first example on using covalent organic frameworks (COFs) as a support and electron-donor for fabricating novel CdS-COF nanocomposite system and its potential application in solar energy transformations.

Facile Preparation and Highly Efficient Catalytic Performances of Pd-Cu Bimetallic Catalyst Synthesized via Seed-Mediated Method.

With the rapid development of industry, the problem of environmental pollution has become increasingly prominent. Exploring and preparing green, efficient, and low cost catalysts has become the key challenge for scientists. However, some conventional preparation methods are limited by conditions, such as cumbersome operation, high energy consumption, and high pollution. Here, a simple and efficient seed-mediated method was designed and proposed to synthesize a highly efficient bimetallic catalyst for catalyzing nitro compounds. A Pd-Cu bimetallic composite (BCM) can be prepared by synthesizing the original seed crystal of precious metal palladium, then growing the mature nanocrystalline palladium and supporting the transition metal copper. Importantly, after eight consecutive catalytic cycles, the conversion of the catalyzed 2-NA was 84%, while the conversion of the catalyzed 4-NP was still 72%. And the catalytic first order rates of 2-NA and 4-NP constants were 0.015 s-1, and 0.069 s-1, respectively. Therefore, current research of nanocomposites catalyst showed great significance for serious environmental pollution problems and the protection of living environment, providing a new idea for the preparation of new bimetallic catalytic materials.

Highly Efficient Catalytic Performances of Nitro Compounds and Morin via Self-Assembled MXene-Pd Nanocomposites Synthesized through Self-Reduction Strategy.

With development of the society, the problem of environmental pollution is becoming more and more serious. There is the urgent need to develop a new type of sustainable green material for degradable pollutants. However, the conventional preparation method is limited by conditions such as cumbersome operation, high energy consumption, and high pollution. Here, a simple method named self-reduction has been proposed, to synthesize highly efficient catalytic nitro compounds and morin self-assembled MXene-Pd nanocomposites. Palladium nanoparticles were grown in situ on MXene nanosheets to form MXene@PdNPs. MXene@PdNPs composites with different reaction times were prepared by adjusting the reduction reaction time. In particular, MXene@PdNPs20 exhibited a high catalytic effect on 4-NP and 2-NA, and the first-order rate constants of the catalysis were 0.180 s-1 and 0.089 s-1, respectively. It should be noted that after eight consecutive catalytic cycles, the conversion to catalyze 4-NP was still greater than 94%, and the conversion to catalyze 2-NA was still greater than 91.8%. Therefore, the research of self-assembled MXene@PdNPs nanocomposites has important potential value for environmental management and sustainable development of human health, and provides new clues for the future research of MXene-based new catalyst materials.

High-Indexed PtNi Alloy Skin Spiraled on Pd Nanowires for Highly Efficient Oxygen Reduction Reaction Catalysis.

The catalytic performance of Pt-based catalysts for oxygen reduction reactions (ORR) can generally be enhanced by constructing high-index exposed facets (HIFs). However, the synthesis of Pt alloyed high-index skins on 1D non-Pt surfaces to further improve Pt utilization and stability remains a fundamental challenge for practical nanocrystals. In this work, Pd nanowires (NWs) are selected as a rational medium to facilitate the epitaxial growth of Pt and Ni. Based on the different nucleation and growth habits of Pt and Ni, a continuous PtNi alloy skin bounded with HIFs spiraled on a Pd core can be obtained. Here, the as-prepared helical Pd@PtNi NWs possess high HIF densities, low Pt contents, and optimized oxygen adsorption energies, demonstrating an enhanced ORR mass activity of 1.75 A mgPt -1 and a specific activity of 3.18 mA cm-2 , which are 10 times and 12 times higher than commercial Pt/C catalysts, respectively. In addition, the 1D nanostructure enables the catalyst to be highly stable after 30 000 potential sweeping cycles. This work successfully extends bulky high-indexed Pt alloys to core-shell nanostructures with the design of a new, highly efficient and stable Pt-based catalyst for fuel cells.

Phase-pure pentlandite Ni4.3Co4.7S8 binary sulfide as an efficient bifunctional electrocatalyst for oxygen evolution and hydrogen evolution.

Developing an efficient non-noble bifunctional electrocatalyst for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in the same electrolyte is significant for lowering the cost of electrochemical water splitting. Herein, a phase-pure pentlandite Ni4.3Co4.7S8 bifunctional electrocatalyst was synthesized via a hydrothermal process using a commercial nickel foam as the nickel source. The active metallic nickel source and the chelating agent ethylenediamine play important roles in the formation of phase-pure pentlandite Ni4.3Co4.7S8 binary sulfide. Physicochemical characterizations, electrochemical measurements and density functional theory (DFT) computations illustrate that the material has an exposed high-indexed (022) surface with a biomimetic hydrogenase-like structure, and that the pentlandite phase has metallic characteristics, with next-nearest neighbor metal-metal bonds, as well as there being a high overlap of density of state (DOS) at the Fermi-level due to the synergistic effect between Ni and Co ions. In addition, there is an elevation of the d-state center (from -2.84 to -1.52 eV) with high occupation of the anti-bonding eg (dx2-y2 and dz2) d-orbitals. These properties endow the Ni4.3Co4.7S8 bifunctional electrocatalyst with higher catalytic activity for OER than RuO2, with comparative activity for HER to commercial Pt/C and with a low over-potential for all water splitting in an alkaline electrolyte. The studies here provide a novel strategy to synthesise phase-pure pentlandite nickel cobalt binary sulfides and boost their applications in electrochemical water splitting.

Monolayer Nickel Cobalt Hydroxyl Carbonate for High Performance All-Solid-State Asymmetric Supercapacitors.

The emergence of atomically thick nanolayer materials, which feature a short ion diffusion channel and provide more exposed atoms in the electrochemical reactions, offers a promising occasion to optimize the performance of supercapacitors on the atomic level. In this work, a novel monolayer Ni-Co hydroxyl carbonate with an average thickness of 1.07 nm is synthesized via an ordinary one-pot hydrothermal route for the first time. This unique monolayer structure can efficiently rise up the exposed electroactive sites and facilitate the surface dependent electrochemical reaction processes, and thus results in outstanding specific capacitance of 2266 F g(-1). Based on this material, an all-solid-state asymmetric supercapacitor is developed adopting alkaline PVA (poly(vinyl alcohol)) gel (PVA/KOH) as electrolyte, which performs remarkable cycling stability (no capacitance fade after 19 000 cycles) together with promising energy density of 50 Wh kg(-1) (202 µWh cm(-2)) and high power density of 8.69 kW kg(-1) (35.1 mW cm(-2)). This as-assembled all-solid-state asymmetric supercapacitor (AASC) holds great potential in the field of portable energy storage devices.

Construction of a novel hierarchical structured NH4-Co-Ni phosphate toward an ultrastable aqueous hybrid capacitor.

Aqueous hybrid capacitors (HCs) suffer from sacrificed power density and long cycle life due to the insufficient electric conductivity and poor chemical stability of the battery-type electrode material. Herein, we report a novel NH4-Co-Ni phosphate with a stable hierarchical structure combining ultrathin nanopieces and single crystal microplatelets in one system, which allows for a synergistic integration of two microstructures with different length scales and different energy storage mechanisms. The microplatelets with a stable single crystal structure store charge through the intercalation of hydroxyl ions, while the ultrathin nanopieces store charge through surface redox reaction providing enhanced specific capacitance. Furthermore, the large single crystal can bridge the small nanopieces forming continuous electronic conduction paths as well as ionic conduction channels, and facilitate both electron and ion transportation in the hierarchical structure. The HC cell based on the as prepared material and a 3D hierarchical porous carbon delivers a high energy density of 29.6 Wh kg(-1) at a high power density of 11 kW kg(-1). Particularly, an ultralong cycle life along with 93.5% capacitance retention after 10,000 charge-discharge cycles is achieved, which is outstanding among the state-of-the-art aqueous HC cells.

Ultrahigh volumetric capacitance and cyclic stability of fluorine and nitrogen co-doped carbon microspheres.

Highly porous nanostructures with large surface areas are typically employed for electrical double-layer capacitors to improve gravimetric energy storage capacity; however, high surface area carbon-based electrodes result in poor volumetric capacitance because of the low packing density of porous materials. Here, we demonstrate ultrahigh volumetric capacitance of 521 F cm(-3) in aqueous electrolytes for non-porous carbon microsphere electrodes co-doped with fluorine and nitrogen synthesized by low-temperature solvothermal route, rivaling expensive RuO2 or MnO2 pseudo-capacitors. The new electrodes also exhibit excellent cyclic stability without capacitance loss after 10,000 cycles in both acidic and basic electrolytes at a high charge current of 5 A g(-1). This work provides a new approach for designing high-performance electrodes with exceptional volumetric capacitance with high mass loadings and charge rates for long-lived electrochemical energy storage systems.