Latest ArticlesAmmonia (NH3), as an important chemical substance and clean energy carrier, plays an indispensable role in industrial and agricultural production. The electrocatalytic synthesis of NH3 under mild conditions has attracted worldwide attention in the energy field due to its environmental friendliness and cost efficiency, but unsatisfactory NH3 yields and Faradaic efficiencies are restricting its development. The introduction of defect has been demonstrated as a feasible way to overcome the disadvantages of electrochemistry, as it can regulate the electronic structure and modulate coordination environment of electrocatalysts, which further create active sites and enhance nitrogen adsorption. In this regard, it is necessary to understand the effects of various types of defects on electrocatalysts based on the latest progress in the defect engineering for nitrogen reduction reaction (NRR). In this review, the concept, classifications, and characterization of defects as well as the approaches to create them in electrocatalysts are firstly discussed. Then, certain types of defects (vacancy, dopant, amorphism, edge/corner, and porousness) affecting the performances of various electrocatalysts are further described. Finally, the summary and challenges of electrocatalytic ammonia synthesis are proposed to design advanced electrocatalysts with high efficiency.
Comprehensive fundamental understanding of CO hydrogenation reactions over Cu and ZnCu alloy surfaces is of great importance. Herein, we report a comparative DFT calculation study of elementary surface reaction network of CO hydrogenation reactions on stepped Cu(211), Cu(611), ZnCu(211) and ZnCu(611) surfaces. On ZnCu(211) and ZnCu(611) surfaces, the energetic favorable reaction path of CO hydrogenation reaction follows CO* → HCO* → H2CO* → H3CO* → CH3OH* → CH3OH with H3CO* hydrogenation as the rate-limiting step and proceeds more facilely on ZnCu(611) surface than on ZnCu(211) surface. On Cu(211) and Cu(611) surfaces, the energetic favorable reaction path of CO hydrogenation reaction follows CO* → HCO* → HCOH* → H2COH* → H3COH* → CH3* → CH4* → CH4 with H2COH* hydrogenation as the rate-limiting step and proceeds more facilely on Cu(611) than on Cu(211). The key difference of CO hydrogenation reaction on ZnCu alloy surface and Cu is that the resulting CH3OH* species desorbs to produce CH3OH on ZnCu alloy but undergoes H*-assisted decomposition to CH3* and eventually to CH4 on Cu surface. These results successfully unveil elementary surface reaction networks and structure sensitivity of Cu and ZnCu alloy-catalyzed CO hydrogenation reactions.
The influence of 1H-benzo[f]indole (Bd) and its derivatives on room temperature phosphorescence (RTP) has raised great concern since they were found to significantly affect RTP of the extensively studied carbazole (Cz) derivatives. However, the role of Bd itself existing in Cz-based or other doping systems was still unclear. In order to clarify its intrinsic phosphorescent property, Bd was introduced as a guest into different organic matrixes including substituted Cz derivatives and polymers. The phosphorescence located in 560–620 nm was confirmed to be derived from Bd itself, which can be detected whatever Bd was doped in the crystal or amorphous state of Cz derivatives. The suitable energy gap between Cz derivatives and Bd is the key to achieve ultralong RTP of Bd. Additionally, when doped in polymers with plenty of hydrogen bonds, RTP of Bd with lifetime over 280 ms was easily obtained. Among them, Bd@PHEMA (poly(hydroxyethyl methacrylate) exhibited superior phosphorescence, with yellow afterglow lasting for over 2.5 s. Therefore, this work demonstrated that a new organic RTP phosphor, Bd, is discovered, and ultralong RTP of Bd can be achieved not only doped in Cz derivatives but also in polymers as the hosts.
We report that the photoinduced dynamics of the phytochrome chromophore is strongly dependent on the protonation/deprotonation states of the pyrrole ring. The on-the-fly surface hopping dynamics simulations were performed to study the photoisomerization of different protonation/deprotonation phytochrome chromophore models. The simulation results indicate that the deprotonations at the pyrrole rings significantly modify the photoinduced nonadiabatic dynamics, leading to distinctive population decay dynamics and different reaction channels. Such feature can be well explained by the formation of the different hydrogen bond network patterns. Therefore, the proper understanding of the photoisomerization mechanism of phytochrome chromophore must take the hydrogen bond network into account. This work provides the new insights into the photobiological functions of phytochrome chromophore and suggests the possible ideas to control of its photoconversion processes for further rational engineering in optical applications.
CO oxidation is a benchmark in heterogeneous catalysis for evaluation of redox catalysts due to its practical relevance in many applications and the fundamental problems associated with its very high activity at low temperatures. Among which, Co3O4 is one of the most active non-precious metal catalysts. Exposed crystal planes and cobalt sites are considered to be important for its high catalytic activity. Herein, we demonstrate an enhanced CO oxidation activity by a defect-rich mesoporous Co3O4 that prepared by a designed dual-template method. Two different kinds of silicas are used as hard-templates at the same time, resulting in a defect-rich mesoporous Co3O4 with a surface area as high as 169 m2/g. This catalyst exhibited a very high catalytic activity for low temperature CO oxidation with a light-off temperature at −73 ℃ under the space velocity of 80,000 mL h-1 gcat-1. Further studies reveal that the high surface area promotes the lattice oxygen mobility, surface rich of Co2+ species and active oxygen species are crucial for the high catalytic activity. Moreover, the dual-template approach paves a way towards the design and construction of high-surface-area mesoporous metal oxides for various applications.
The accurate delivery of nanoparticles and organic small molecule drugs remains a serious challenge in nanoparticle-based tumor therapy. Dual-targeted therapy combining tumor cell targeting and organelle targeting is an effective solution. Here, an anticancer nanoformulation accurate delivery system was prepared using hyaluronic acid (HA) targeting CD44 receptors on the surface of tumor cells and IR780 iodine (IR780) targeting mitochondrial for delivery. The system is based on an ultra-small Janus structured inorganic sensitizer TiO2-x@NaGdF4 nanoparticles (TN NPs) prepared by one-step pyrolysis, further loaded with organic small molecule acoustic sensitizer IR780 and mitochondrial hexokinase Ⅱ inhibitor lonidamine (LND), followed by encapsulation of HA. Ultra-small size nanoparticles exhibit strong tissue penetration, tumor inhibition and in vivo metabolism. Under ultrasound radiation, TN NPs and IR780 could produce a synergistic effect, effectively increased the efficiency of reactive oxygen species (ROS) production. Meanwhile, the released IR780 could smoothly target the mitochondria, and the ROS produced by IR780 can destroy the mitochondrial structure and disrupt the mitochondrial respiration. LND could inhibit the energy metabolism of tumor cells by reducing the activity of hexokinase Ⅱ (HK Ⅱ), which further accelerates the process of apoptosis. Furthermore, since the Janus structure allows the integration of multifunctional components into a single system, TN NPs can not only serve as an acoustic sensitizer to generate ROS, but the Gd element contained can also act as the nuclear magnetic resonance (MR) imaging contrast agent, suggesting that the nanoformulation can enable imaging-guided diagnosis and therapy. In conclusion, a new scheme to enhance sonodynamic therapy (SDT) and chemotherapy synergistically is proposed here based on ultra-small dual-targeted nanoformulation with Janus structure in the ultrasound radiation environment.
Owing to the further requirement for electric vehicle market, it is appropriate to lower the cost and improve the energy density of lithium-ion batteries by adopting the Co-free and Ni-rich layered cathodes. However, their practical application is severely limited by structural instability and slow kinetics. Herein, ultrahigh-nickel cobalt-free LiNi0.9Mn0.1O2 cathode is elaborate designed via in-situ trace substitution of tungsten by a wet co-precipitation method following by high-temperature sintering. It is revealed that the in-situ doping strategy of high valence W6+ can effectively improve the structure stability by reducing irreversible phase transition and suppressing the formation of microcracks. Moreover, the transformed fine particles determined by W-doping can facilitate the kinetic characteristics by shortening Li+ diffusion paths. As expected, 0.3 mol% W-doped LiNi0.9Mn0.1O2 cathode exhibits a high specific capacity of 143.5 mAh/g after 200 cycles at high rate of 5 C in the wide potential range of 2.8-4.5 V, representing a potential next-generation cathode with low-cost, high energy-density and fast-charging capabilities.
The integration of lanthanide (Ln) ions and polyoxoniobates (PONbs) is challenging, and the known Ln-substituted PONbs are still scarce. This work introduces high-nuclear iso-Ln-oxo clusters into the PONb system. The first series of high-nuclear Ln-oxo clusters encapsulated heterometallic polyoxoniobates H9[Na(H2O)4][Cu(en)2]10{Ln6(μ3-OH)6(SiNb18O54)3}·18H2O (1-Ln, en = ethylenediamine, Ln = Dy, Gd, Tb, Ho, Er, Tm, Yb, Lu) based on flower-like {Ln6(μ3-OH)6(SiNb18O54)3} ({Ln6Si3Nb54}) clusters have been successfully synthesized via one-pot hydrothermal synthesis strategy. The flower-like polyoxoanion {Ln6Si3Nb54} is consisted of three heteropolyoxoniobate {SiNb18O54} clusters and one unique planar equilateral triangle-shaped {Ln6(μ3-OH)6} cluster, which presents the highest nuclear iso-Ln-oxo cluster in PONb chemistry. In {Ln6(μ3-OH)6} cluster, each pair of μ3-OH groups link three Dy3+ ions to form a small approximate equilateral triangle-shaped {Dy3(OH)2} cluster. Furthermore, the three {Dy3(OH)2} clusters comprise a bigger approximate equilateral triangle-shaped {Dy6(μ3-OH)6} cluster. The reported hexanuclear {Ln6} cluster skeletons are mostly octahedral, however, such equilateral triangle-shaped skeleton of the hexanuclear Ln-oxo cluster is first observed. The 1-Dy exhibits good water vapor adsorption capacity and ferromagnetic properties.
Localized high-concentration electrolytes (LHCE) have shown good compatibility with high-voltage lithium (Li)-metal batteries, but their practicality is yet to be proved in terms of cost and safety. Here we develop a hybrid-LHCE with favorable integrated properties by combining the merits of two representative diluents, fluorobenzene (FB) and 1, 1, 2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether (TFE). Specifically, the extremely cheap and lightweight FB significantly reduces the cost and density of electrolyte, while the fire-retardant TFE circumvents the flammable nature of FB and thus greatly improves the safety of electrolyte. Moreover, the FB–TFE mixture enhances the thermodynamic stability of hybrid-LHCE and renders a controllable defluorination of FB, contributing to the formation of a thin and durable inorganic-rich solid electrolyte interphase (SEI) with rapid ion-transport kinetics. Benefiting from the designed hybrid-LHCE, a Li|NCM523 battery demonstrates excellent cycling performance (215 cycles, 91% capacity retention) under challenging conditions of thin Li-anode (30 µm) and high cathode loading (3.5 mAh/cm2).
Free-standing electrodes are promising candidates for flexible rechargeable batteries, toward the application of flexible energy storage devices, due to their merits of additive-free, lightweight, and high energy density. Herein, we report a free-standing SnNb2O6@CSN flexible film with SnNb2O6 encapsulated in 3D carbon skeleton nanofibers by electrospinning and carbonization processes as flexible anode for sodium-ion batteries (SIBs). The 3D carbon skeleton nanofibers serve as ion/electron transport pathway to improve the electrochemical reaction kinetics and meanwhile alleviate the volume changes of SnNb2O6 during charge-discharge processes. The as-constructed half-cell (SnNb2O6@CSN‖Na) exhibits excellent cycling stability of 99.2 mAh/g at 0.5 A/g after 950 cycles (coulombic efficiency of ~100%) and a high rate performance of 108.6 mAh/g at 10 A/g. In addition, the pouch cell can light up the LEDs at different bending angles (0°, 90°, 180°). This research shows a promising anode material for flexible energy storage electronics.
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