Pd(II) coordination molecule modified g-C3N4 for boosting photocatalytic hydrogen production.

The photocatalytic H2 production activity of polymer carbon nitride (g-C3N4) is limited by the rapid recombination of photoelectron-hole pairs and slow surface reduction dynamic process. Here, a supramolecular complex (named R-TAP-Pd(II)) was fabricated via self-assembly of (R)-N-(1-phenylethyl)-4-(4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)benzamide (R-TAP) with Pd(II) and used to modify g-C3N4. In the R-TAP-Pd(II)@g-C3N4 composite photocatalyst, the spin polarization of R-TAP-Pd(II) can promote charge transfer and inhibit photogenerated carrier recombination, as confirmed by spectral tests and photoelectrochemical performance tests. Electrochemical tests and in situ X-ray photoelectron spectroscopy (XPS) tests proved that the Pd(II) ion in the R-TAP-Pd(II) molecule can serve as active sites to accelerate H2 production. The R-TAP-Pd(II)@g-C3N4 presented a photocatalytic H2 generation rate of 1085 µmol g-1 h-1 when exposed to visible light, which was a about 278-fold increase compared with g-C3N4. This work finds a new approach to boost the photocatalytic efficiency of g-C3N4 via supramolecular self-assembly.

Metal Organic Frameworks as Polysulfide Reaction Modulators for Lithium Sulfur Batteries: Advances and Perspectives.

Currently, lithium sulfur (Li-S) battery with high theoretical energy density has attracted great research interest. However, the diffusion and loss process of intermediate lithium polysulfide during charge-discharge hindered the application of the Li-S battery in modern life. To overcome this issue, metal organic frameworks (MOFs) and their composites have been regarded as effective additions to restrain the LiPS diffusion process for Li-S battery. Benefiting from the unique structure with rich active sites to adsorb LiPS and accelerate the LiPS redox, the Li-S batteries with MOFs modified exhibit superior electrochemical performance. Considering the rapid development of MOFs in Li-S battery, this review summarizes the recent studies of MOFs and their composites as the sulfur host materials, functional interlayer, separator coating layer, and separator/solid electrolyte for Li-S batteries in detail. In addition, the promising design strategies of functional MOF materials are proposed to improve the electrochemical performance of Li-S battery.

In suit constructing S-scheme FeOOH/MgIn2S4 heterojunction with boosted interfacial charge separation and redox activity for efficiently eliminating antibiotic pollutant.

Photocatalytic elimination of antibiotic pollutant is an appealing avenue in response to the water contamination, but it still suffers from sluggish charge detachment, limited redox capacity as well as poor visible light utilization. Herein, a particular S-scheme FeOOH/MgIn2S4 heterojunction with wide visible light absorption was triumphantly constructed by in-situ growth of MgIn2S4 nanoparticles onto the surface of FeOOH nanorods, and employed as a high-efficiency visible light driven photocatalyst for removing tetracycline (TC). Conspicuously, the as-obtained FeOOH(15 wt%)/MgIn2S4 elucidated the optimal TC removal rate of 0.01258 min-1 after 100 min of visible light illumination, which was almost 33.1 and 6.6 times larger than those of neat FeOOH and MgIn2S4, separately. The exceptional degradation performance was principally put down to the establishment of S-scheme heterojunction between FeOOH and MgIn2S4, which could not merely accelerate the detachment of photogenerated carriers, but also retain the powerful reducing ability of photoinduced electrons for MgIn2S4 and high oxidizing capacity of photoexcited holes for FeOOH, strongly driving the generation of plentiful active species including holes, superoxide and hydroxyl radicals. Additionally, the possible degradation mechanism and pathways of TC were also speculated. This work offers a valuable perspective for constructing high-efficiency S-scheme heterojunction photocatalysts for eradicating antibiotics.

Boosting CdS Photocatalytic Activity for Hydrogen Evolution in Formic Acid Solution by P Doping and MoS2 Photodeposition.

Formic acid is an appealing hydrogen storage material. In order to rapidly produce hydrogen from formic acid under relatively mild conditions, high-efficiency and stable photocatalytic systems are of great significance to prompt hydrogen (H2) evolution from formic acid. In this paper, an efficient and stable photocatalytic system (CdS/P/MoS2) for H2 production from formic acid is successfully constructed by elemental P doping of CdS nanorods combining with in situ photodeposition of MoS2. In this system, P doping reduces the band gap of CdS for enhanced light absorption, as well as promoting the separation of photogenerated charge carriers. More importantly, MoS2 nanoparticles decorated on P-doped CdS nanorods can play as noble-metal-free cocatalysts, which increase the light adsorption, facilitate the charge transfer and effectively accelerate the hydrogen evolution reaction. Consequently, the apparent quantum efficiency (AQE) of the designed CdS/P/MoS2 is up to 6.39% at 420 nm, while the H2 evolution rate is boosted to 68.89 mmol·g-1·h-1, which is 10 times higher than that of pristine CdS. This study could provide an alternative strategy for the development of competitive CdS-based photocatalysts as well as noble-metal-free photocatalytic systems toward efficient hydrogen production.

In Situ Photodeposited Construction of Pt-CdS/g-C3N4-MnOx Composite Photocatalyst for Efficient Visible-Light-Driven Overall Water Splitting.

For converting the renewable solar energy to hydrogen (H2) energy by photocatalytic (PC) overall water splitting (OWS), visible-light-driven photocatalysts are especially desired. Herein, a model CdS/g-C3N4 photocatalyst with a type II heterojunction is first demonstrated via a facile coupling of g-C3N4 nanosheets and CdS nanorods. After being combined with in situ photodeposited 3 wt % Pt and 4 wt % MnOx dual cocatalysts simultaneously, the optimal visible-light-driven (λ > 400 nm) composite photocatalyst of Pt-CdS/g-C3N4-MnOx gives a H2 generation rate of 9.244 µmol h-1 (924.4 µmol h-1 g-1) and a O2 evolution rate of 4.6 µmol h-1 (460 µmol h-1 g-1) in pure water, which is over 420 times higher than that of pure CdS nanorods loaded with 0.5 wt % Pt. The apparent quantum efficiency (AQE) reaches about 3.389% (at 400 nm) and 1.745% (at 420 nm), respectively. The combination of a type II heterojunction and simultaneous in situ photodeposition of the dual cocatalysts results in a dramatically improved PC efficiency and a long-term stability of the CdS/g-C3N4 visible-light-driven photocatalyst for OWS.

Modified Graphitic Carbon Nitride Nanosheets for Efficient Photocatalytic Hydrogen Evolution.

Considerable research efforts have been devoted to develop noble-metal-free cocatalysts coupled with semiconductors for highly efficient photocatalytic H2 evolution as part of the challenge toward solar-to-fuel conversion. Herein, a new cocatalyst with excellent activity in the electrocatalytic H2 evolution reaction (HER) that is based on Co sheathed in N-doped graphitic carbon nanosheets (Co@NC) was fabricated by a surfactant-assisted pyrolysis approach and then coupled with g-C3 N4 nanosheets to construct a 2 D-2 D g-C3 N4 /Co@NC composite photocatalyst by a simple grinding method. As a result of advantages in effective electrocatalytic HER activity, suitable electronic band structure, and rapid interfacial charge transfer brought about by the 2 D-2 D spatial configuration, the g-C3 N4 /Co@NC photocatalyst that contained 4 wt % Co@NC presented a high photocatalytic H2 generation rate of 15.67 µmol h-1 under visible-light irradiation (λ≥400 nm), which was 104.5 times higher than that of pristine g-C3 N4 . The optimum g-C3 N4 /Co@NC photocatalyst showed a high apparent quantum efficiency of 10.82 % at λ=400 nm.

Tin dioxide@carbon core-shell nanoarchitectures anchored on wrinkled graphene for ultrafast and stable lithium storage.

The SnO2@C@GS composites as a new type of 3D nanoarchitecture have been successfully synthesized by a facile hydrothermal process followed by a sintering strategy. Such a 3D nanoarchitecture is made up of SnO2@C core-shell nanospheres and nanochains anchored on wrinkled graphene sheets (GSs). Transmission electron microscopy shows that these core-shell nanoparticles consist of 3-9 nm diameter secondary SnO2 nanoparticles embedded in about 50 nm diameter primary carbon nanospheres. Large quantities of core-shell nanoparticles are uniformly attached to the surface of wrinkled graphene nanosheets, with a portion of them further connected into nanochains. This new 3D nanoarchitecture consists of two different kinds of carbon-buffering matrixes, i.e., the carbon layer produced by glucose carbonization and the added GS template, leading to enhanced lithium storage properties. The lithium-cycling properties of the SnO2@C@GS composite have been evaluated by galvanostatic discharge-charge cycling and electrochemical impedance spectroscopy. Results show that the SnO2@C@GS composite has discharge capacities of 883.5, 845.7, and 830.5 mA h g(-1) in the 20th, 50th and 100th cycles, respectively, at a current density of 200 mA g(-1) and delivers a desirable discharge capacity of 645.2 mA h g(-1) at a rate of 1680 mA g(-1). This new 3D nanoarchitecture exhibits a high capability and excellent cycling and rate performance, holding great potential as a high-rate and stable anode material for lithium storage.

Topological morphology conversion towards SnO2/SiC hollow sphere nanochains with efficient photocatalytic hydrogen evolution.

Novel SnO2/SiC hollow sphere nanochains were synthesized by topological morphology conversion of SnO2@C core-shell nanochains through a vapour-solid reaction. Evaluation of the SnO2/SiC HSNCs for the generation of hydrogen revealed that they exhibit excellent catalytic activity and durability.