Interfacial Engineering Boosting the Activity and Stability of MIL-53(Fe) toward Electrocatalytic Nitrogen Reduction.

The electrochemical nitrogen reduction reaction (eNRR) has emerged as a promising strategy for green ammonia synthesis. However, it suffers unsatisfactory reaction performance owing to the low aqueous solubility of N2 in aqueous solution, the high dissociation energy of N≡N, and the unavoidable competing hydrogen evolution reaction (HER). Herein, a MIL-53(Fe)@TiO2 catalyst is designed and synthesized for highly efficient eNRR. Relative to simple MIL-53(Fe), MIL-53(Fe)@TiO2 achieves a 2-fold enhancement in the Faradaic efficiency (FE) with an improved ammonia yield rate by 76.5% at -0.1 V versus reversible hydrogen electrode (RHE). After four cycles of electrocatalysis, MIL-53(Fe)@TiO2 can maintain a good catalytic activity, while MIL-53(Fe) exhibits a significant decrease in the NH3 yield rate and FE by 79.8 and 82.3%, respectively. Benefiting from the synergetic effect between TiO2 and MIL-53(Fe) in the composites, Fe3+ ions can be greatly stabilized in MIL-53(Fe) during the eNRR process, which greatly hinders the catalyst deactivation caused by the electrochemical reduction of Fe3+ ions. Further, the charge transfer ability in the interface of composites can be improved, and thus, the eNRR activity is significantly boosted. These findings provide a promising insight into the preparation of efficient composite electrocatalysts.

Photocatalytic Conversion of Diluted CO2 into Tunable Syngas via Modulating Transition Metal Hydroxides.

The conversion of diluted CO2 into tunable syngas via photocatalysis is critical for implementing CO2 reduction practically, although the efficiency remains low. Herein, we report the use of graphene-modified transition metal hydroxides, namely, NiXCo1-X-GR, for the conversion of diluted CO2 into syngas with adjustable CO/H2 ratios, utilizing Ru dyes as photosensitizers. The Ni(OH)2-GR cocatalyst can generate 12526 µmol g-1 h-1 of CO and 844 µmol g-1 h-1 of H2, while the Co(OH)2-GR sample presents a generation rate of 2953 µmol g-1 h-1 for CO and 10027 µmol g-1 h-1 for H2. Notably, by simply altering the addition amounts of nickel and cobalt in the transition metal composite, the CO/H2 ratios in syngas can be easily regulated from 18:1 to 1:4. Experimental characterization of composites and DFT calculations suggest that the differing adsorption affinities of CO2 and H2O over Ni(OH)2-GR and Co(OH)2-GR play a significant role in determining the selectivity of CO and H2 products, ultimately affecting the CO/H2 ratios in syngas. Overall, these findings demonstrate the potential of graphene-modified transition metal hydroxides as efficient photocatalysts for CO2 reduction and syngas production.

High-efficiency visible-light-driven oxidation of primary C-H bonds in toluene over a CsPbBr3 perovskite supported by hierarchical TiO2 nanoflakes.

Photocatalytic oxidation of toluene to valuable fine chemicals is of great significance, yet faces challenges in the development of advanced catalysts with both high activity and selectivity for the activation of inert C(sp3)-H bonds. Halide perovskites with remarkable optoelectronic properties have shown to be prospective photoactive materials, but the bulky structure with a small surface area and severe recombination of photogenerated electron-hole pairs are obstacles to application. Here, we fabricate a hierarchical nanoflower-shaped CsPbBr3/TiO2 heterojunction by assembling CsPbBr3 nanoparticles on 2D TiO2 nanoflake subunits. The design significantly downsizes the size of CsPbBr3 from micrometers to nanometers, and forms a type II heterojunction with intimate interfacial contact between CsPbBr3 and TiO2 nanoflakes, thereby accelerating the separation and transfer of photogenerated charges. Moreover, the formed hierarchical heterojunction increaseslight absorption by refraction and scattering, offers a large surface area and enhances the adsorption of toluene molecules. Consequently, the optimized CsPbBr3/TiO2 exhibits a high performance (10 200 µmol g-1 h-1) for photocatalytic toluene oxidation with high selectivity (85%) for benzaldehyde generation under visible light. The photoactivity is about 20 times higher than that of blank CsPbBr3, and is among the best photocatalytic performances reported for selective oxidation of toluene under visible light irradiation.

Photocatalytic Anaerobic Dehydrogenation of Alcohols over Metal Halide Perovskites: A New Acid-Free Scheme for H2 Production.

Photocatalytic H2 evolution from haloid acid (HX) solution by metal halide perovskites (MHPs) has been intensively investigated; however, the corrosive acid solution severely restricts its practical operability. Therefore, developing acid-free schemes for H2 evolution using MHPs is highly desired. Here, we investigate the photocatalytic anaerobic dehydrogenation of alcohols over a series of MHPs (APbX3, A = Cs+, CH3NH3+ (MA), CH(NH2)2+ (FA); X = Cl-, Br-, I-) to simultaneously produce H2 and aldehydes. Via the coassembly of Pt and rGO nanosheets on MAPbBr3 microcrystals, the optimal MAPbBr3/rGO-Pt reaches a H2 evolution rate of 3150 µmol g-1 h-1 under visible light irradiation (780 nm ≥ λ ≥ 400 nm), which is more than 105-fold higher than pure MAPbBr3 (30 µmol g-1 h-1). The present work not only brings new ample opportunities toward photocatalytic H2 evolution but also opens up new avenues for more effective utilization of MHPs in photocatalysis.

Ultrathin Two-Dimensional ZnIn2S4/Nix-B Heterostructure for High-Performance Photocatalytic Fine Chemical Synthesis and H2 Generation.

Photocatalytic H2 evolution coupled with organic transformation provides a new avenue to cooperatively produce clean fuels and fine chemicals, enabling a more efficient conversion of solar energy. Here, a novel two-dimensional (2D) heterostructure of ultrathin ZnIn2S4 nanosheets decorated with amorphous nickel boride (Nix-B) is prepared for simultaneous photocatalytic anaerobic H2 generation and aromatic aldehydes production. This ZnIn2S4/Nix-B catalyst elaborately combines the ultrathin structure advantage of the ZnIn2S4 semiconductor and the cocatalytic function of Nix-B. A high H2 production rate of 8.9 mmol h-1 g-1 is delivered over the optimal ZnIn2S4/Nix-B with a stoichiometric production of benzaldehyde, which is about 22 times higher than ZnIn2S4. Especially, the H2 evolution rate is much higher than the value (2.8 mmol h-1 g-1) of the traditional photocatalytic half reaction of H2 production with triethanolamine as a sacrificial agent. The apparent quantum yield reaches 24% at 420 nm, representing an advanced photocatalyst system. Moreover, compared with traditional sulfide, hydroxide, and even noble metal modified ZnIn2S4/M counterparts (M = NiS, Ni(OH)2, Pt), the ZnIn2S4/Nix-B also maintains markedly higher photocatalytic activity, showing a highly efficient and economical advantage of the Nix-B cocatalyst. This work sheds light on the exploration of 2D ultrathin semiconductors decorated with novel transition metal boride cocatalyst for efficient photocatalytic organic transformation integrated with solar fuel production.

Alkaline Co(OH)2-Decorated 2D Monolayer Titanic Acid Nanosheets for Enhanced Photocatalytic Syngas Production from CO2.

The difficulty of adsorption and activation of CO2 at the catalytic site and rapid recombination of photogenerated charge carriers severely restrict the CO2 conversion efficiency. Here, we fabricate a novel alkaline Co(OH)2-decorated ultrathin 2D titanic acid nanosheet (H2Ti6O13) catalyst, which rationally couples the structural and functional merits of ultrathin 2D supports with catalytically active Co species. Alkaline Co(OH)2 beneficially binds and activates CO2 molecules, while monolayer H2Ti6O13 acts as an electron relay that bridges a photosensitizer with Co(OH)2 catalytic sites. As such, photoexcited charges can be efficiently channeled from light absorbers to activated CO2 molecules through the ultrathin hybrid Co(OH)2/H2Ti6O13 composite, thereby producing syngas (CO/H2 mixture) from photoreduction of CO2. High evolution rates of 56.5 µmol h-1 for CO and 59.3 µmol h-1 for H2 are achieved over optimal Co(OH)2/H2Ti6O13 by visible light illumination. In addition, the CO/H2 ratio can be facilely tuned from 1:1 to 1:2.4 by changing the Co(OH)2 content, thus presenting a feasible approach to controllably synthesize different H2/CO mixtures for target applications.

Facet Engineering of Pd Nanocrystals for Enhancing Photocatalytic Hydrogenation: Modulation of the Schottky Barrier Height and Enrichment of Surface Reactants.

Metal cocatalyst loading is one of the most widely explored strategies in promoting photocatalytic solar energy conversion. Engineering surface-active facets of metal cocatalyst and exploring how they modulate the reactivity is crucial for the further development of advanced photocatalysts. In this work, through controlled hybridization of two-dimensional (2D) TiO2 nanosheets with well-designed Pd nanocube (Pd NC) with exposed {100} facet and Pd nano-octahedron (NO) with exposed {111} facet, we unravel the distinct crystal facet effect of Pd cocatalyst in promoting the selective hydrogenation of nitroarenes to amines of TiO2 photocatalyst. The activity tests show that the Pd NO with {111} facet is a more efficient cocatalyst than the Pd NC with exposed {100} facet. The prepared TiO2-Pd NO composite displays a 900% enhancement of photocatalytic hydrogenation rate in comparison with bare TiO2, while the TiO2-Pd NC sample only shows a 200% photoactivity enhancement. Microscopic mechanism study discloses that the distinctive photoactivity improvement of Pd NO is ascribed to the concurrent modulation of the Schottky barrier height and enrichment of surface reactants: (i) the Pd NO with a lower Fermi level could result in steeper band bending of TiO2 (i.e., higher Schottky barrier) than the Pd NC, which is more efficient in boosting interfacial separation and inhibiting the recombination of photoexcited charge pairs; and (ii) the {111} facet of Pd has higher nitroarenes adsorption ability and especially stronger hydrogen enrichment capability, thus accelerating the surface hydrogenation process and contributing to a higher reaction rate. This work emphasizes the rational facet control of cocatalysts for enhancing the photocatalytic hydrogenation performance.

Seed-Assisted Synthesis of Graphene Films on Insulating Substrate.

Synthesizing graphene at a large-scale and of high quality on insulating substrate is a prerequisite for graphene applications in electronic devices. Typically, graphene is synthesized and then transferred to the proper substrate for subsequent device preparation. However, the complicated and skilled transfer process involves some issues such as wrinkles, residual contamination and breakage of graphene films, which will greatly degrade its performance. Direct synthesis of graphene on insulating substrates without a transfer process is highly desirable for device preparation. Here, we report a simple, transfer-free method to synthesize graphene directly on insulating substrates (SiO2/Si, quartz) by using a Cu layer, graphene oxide and Poly (vinyl alcohol) as the catalyst, seeds and carbon sources, respectively. Atomic force microscope (AFM), scanning electronic microscope (SEM) and Raman spectroscopy are used to characterize the interface of insulating substrate and graphene. The graphene films directly grown on quartz glass can attain a high transmittance of 92.8% and a low sheet resistance of 620 Ω/square. The growth mechanism is also revealed. This approach provides a highly efficient method for the direct production of graphene on insulating substrates.

Germanium Sub-Microspheres Synthesized by Picosecond Pulsed Laser Melting in Liquids: Educt Size Effects.

Pulsed laser melting in liquid (PLML) has emerged as a facile approach to synthesize submicron spheres (SMSs) for various applications. Typically lasers with long pulse durations in the nanosecond regime are used. However, recent findings show that during melting the energy absorbed by the particle will be dissipated promptly after laser-matter interaction following the temperature decrease within tens of nanoseconds and hence limiting the efficiency of longer pulse widths. Here, the feasibility to utilize a picosecond laser to synthesize Ge SMSs (200~1000 nm in diameter) is demonstrated by irradiating polydisperse Ge powders in water and isopropanol. Through analyzing the educt size dependent SMSs formation mechanism, we find that Ge powders (200~1000 nm) are directly transformed into SMSs during PLML via reshaping, while comparatively larger powders (1000~2000 nm) are split into daughter SMSs via liquid droplet bisection. Furthermore, the contribution of powders larger than 2000 nm and smaller than 200 nm to form SMSs is discussed. This work shows that compared to nanosecond lasers, picosecond lasers are also suitable to produce SMSs if the pulse duration is longer than the material electron-phonon coupling period to allow thermal relaxation.