Domino Effect: Gold Electrocatalyzing Lithium Reduction to Accelerate Nitrogen Fixation.

Green production of NH3 , especially the Li-mediated electrochemical N2 reduction reaction (NRR) in non-aqueous solutions, is attracting research interest. Controversies regarding the NRR mechanism greatly impede its optimization and wide applications. To understand the electrocatalytic process, we treated Au coated carbon fibrous paper (Au/CP) as the model catalyst. In situ XRD confirmed the transformation of lithium intermediates during NRR. Au greatly improved electron transfer kinetics to catalyze metallic Li formation, and accordingly highly accelerated spontaneous NRR. The Faradaic efficiency of NRR on Au/CP reached 34.0 %, and NH3 yield was as high as 50 µg h-1 cm-2 . Our research shows that the key step of Li-mediated non-aqueous NRR is electrocatalytic Li reduction and offers a novel electrocatalyst design method for Li reduction.

Developing carbon-nitride nanosheets for mode-locking ytterbium fiber lasers.

Graphitic carbon nitrides (CNs) have appeared as a new type of photocatalyst for water splitting, but their optical properties (e.g., nonlinear absorption), to the best of our knowledge, have been seldom explored. Here, we report the saturable absorption effects of novel 2D carbon-nitride-type nanosheets and use them as saturable absorbers to passively mode-lock Yb-doped fiber lasers. The CN-based saturable absorber is manufactured by solution coating of 2D CN nanosheets on a gold mirror and has a modulation depth and saturation intensity of 12.5% and 7.5 MW/cm2, respectively. Two different output couplers are employed to construct ring laser cavities. With the 10% coupler, the mode-locked fiber laser produces pulses with duration of ∼310 ps, average power of 1.24 mW, and repetition rate of 7.65 MHz. The laser spectrum is centered at 1066 nm with a bandwidth of 2.4 nm. Increasing the coupling ratio to 50% improves the output power to 2.58 mW but at the same time broadens the pulse width to 420 ps. As a new kind of 2D material with strong saturable absorption, CN nanosheets will open a new way for novel photonic and optoelectronic devices.

An all-inorganic lead halide perovskite-based photocathode for stable water reduction.

Lead halide perovskites (LHPs) have been investigated for photoelectrochemical hydrogen generation from water splitting. However, the harsh requirements in preparing the environment, i.e. isolating water and oxygen, hinder the wide applications of lead halide perovskites. Herein, an all-inorganic perovskite, i.e. a CsPbBr3-based photocathode, has been prepared to generate hydrogen. It is notable that as a valuable trial for a potential large-scale production, the whole preparation process was completed in an open-air environment. The LHP photocathode achieved the highest photocurrent of about 1.2 mA cm-2 at 0 VRHE. And the photocurrent remains around 94% after continuous illumination for 1 h with the Faradaic efficiency of 90%, illustrating a good photoelectrochemical stability. The all-inorganic LHP photocathodes are facile to prepare with a relatively good performance, and can be improved via band engineering and structure optimization, of which large-scale applications can be expected.

2D bismuthene fabricated via acid-intercalated exfoliation showing strong nonlinear near-infrared responses for mode-locking lasers.

The rediscovery of black phosphorus (BP) has expanded the 2D family into Group 15 (Nitrogen Group) elements, among which bismuthene is the latest member with extraordinary opto-electronic, catalytic and biocompatible properties and potential as a 2D topological insulator. However, bulk Bi is not easily mechanically exfoliated as its counterpart of BP. Thus, to date, the reports on 2D Bi fabrication are rare, and investigations on its nonlinear optical properties are even less. Herein, we rationally designed a new strategy combining acid-interaction and liquid exfoliation to successfully transform metal bulk Bi into few-layer semiconductor, which resulted in unseen opto-electronic properties, such as tunable nonlinear responses all the way to the near-infrared (NIR) region. This band is critical for telecommunication and military purposes, but currently, functioning materials are extremely scarce. The origin of this strong saturable absorption was thoroughly explored through time-resolved spectroscopy spanning from the fs to µs timescale, which indicated ultrafast fs to ps carrier dynamics in the early stage and long exciton bleaching recovery up to µs. As a proof-of-concept application, the as-prepared 2D Bi was employed as a saturable absorber to mode-lock a Tm-doped fiber laser and successfully realized a 2 µm NIR-wavelength output. This study not only offers an effective and scalable method to fabricate the new 2D family member bismuthene with extraordinary stability, but also explores its strong and broad nonlinear responses extending into the NIR region and fundamental photoinduced dynamics, which demonstrate the full potential of 2D Bi for application in opto-electronic devices and nonlinear optics.

Solvent-Free Mechanosynthesis of Composition-Tunable Cesium Lead Halide Perovskite Quantum Dots.

A facile and green mechanosynthesis strategy free of solvent and high reaction temperature was developed to fabricate highly emissive cesium lead halide perovskite (CsPbX3) quantum dots (QDs). Their composition can be adjusted conveniently simply through mechanically milling/grinding stoichiometric combinations of raw reagents, thereby introducing a broad luminescence tunability of the product with adjustable wavelength, line width, and photoluminescence quantum yield. Desired CsPbX3 QDs "library" can thus be readily constructed in a way like assembling Lego building blocks. Hence, the method offered new avenues in the preparation of multicomponent cocrystals, adding one appealing apparatus to the tool box of perovskite-type QDs synthesis. Intriguingly, photoinduced dynamic study revealed the hole-transfer process of the as-prepared QDs toward electron donors, indicative of their potential in charge-transfer-based applications such as light-harvesting devices and photocatalysis.

Preparation of large size, few-layer black phosphorus nanosheets via phytic acid-assisted liquid exfoliation.

Ultrathin uniform BP nanosheets with lateral dimensions of up to several tens of micrometers were prepared via a small molecule-assisted liquid phase exfoliation method, which exhibited attractive electron accepting abilities from photosensitizers and was thus promising in diverse applications such as photocatalysis and photovoltaics.

Iron-Doped Carbon Nitride-Type Polymers as Homogeneous Organocatalysts for Visible Light-Driven Hydrogen Evolution.

Graphitic carbon nitrides have appeared as a new type of photocatalyst for water splitting, but their broader and more practical applications are oftentimes hindered by the insolubility or difficult dispersion of the material in solvents. We herein prepared novel two-dimensional (2D) carbon nitride-type polymers doped by iron under a mild one-pot method through preorganizing formamide and citric acid precursors into supramolecular structures, which eventually polycondensed into a homogeneous organocatalyst for highly efficient visible light-driven hydrogen evolution with a rate of ∼16.2 mmol g(-1) h(-1) and a quantum efficiency of 0.8%. Laser photolysis and electrochemical impedance spectroscopic measurements suggested that iron-doping enabled strong electron coupling between the metal and the carbon nitride and formed unique electronic structures favoring electron mobilization along the 2D nanomaterial plane, which might facilitate the electron transfer process in the photocatalytic system and lead to efficient H2 evolution. In combination with electrochemical measurements, the electron transfer dynamics during water reduction were depicted, and the earth-abundant Fe-based catalyst may open a sustainable strategy for conversion of sunlight into hydrogen energy and cope with current challenging energy issues worldwide.

Small molecule-assisted fabrication of black phosphorus quantum dots with a broadband nonlinear optical response.

Ultrathin BP QDs with a uniform size of ∼3.4 nm were prepared via small molecule-assisted liquid phase exfoliation and they exhibited superior broadband nonlinear saturable absorption promising for nonlinear optical applications. Laser photolysis measurement implied that the nonlinear response origin was related to the long-lived electron-hole pairs delocalized within the BP QDs.