Hong-Li Guo

Biomass-Derived Sponge-like Carbonaceous Hydrogels and Aerogels for Supercapacitors

As a newly developed material, carbon gels have been receiving considerable attention due to their multifunctional properties. Herein, we present a facile, green, and template-free route toward sponge-like carbonaceous hydrogels and aerogels by using crude biomass, watermelon as the carbon source. The obtained three-dimensional (3D) flexible carbonaceous gels are made of both carbonaceous nanofibers and nanospheres. The porous carbonaceous gels (CGs) are highly chemically active and show excellent mechanical flexibility which enable them to be a good scaffold for the synthesis of 3D composite materials. We synthesized the carbonaceous gel-based composite materials by incorporating Fe3O4 nanoparticles into the networks of the carbonaceous gels. The Fe3O4/CGs composites further transform into magnetite carbon aerogels (MCAs) by calcination. The MCAs keep the porous structure of the original CGs, which allows the sustained and stable transport of both electrolyte ions and electrons to the electrode surface, leading to excellent electrochemical performance. The MCAs exhibit an excellent capacitance of 333.1 F·g(-1) at a current density of 1 A·g(-1) within a potential window of -1.0 to 0 V in 6 M KOH solution. Meanwhile, the MCAs also show outstanding cycling stability with 96% of the capacitance retention after 1000 cycles of charge/discharge. These findings open up the use of low-cost elastic carbon gels for the synthesis of other 3D composite materials and show the possibility for the application in energy storage.

Coexistence of adsorption and coagulation processes of both arsenate and NOM from contaminated groundwater by nanocrystallined Mg/Al layered double hydroxides.

In this study, nanocrystallined Mg/Al layered double hydroxides (LDH-CO3) and chloridion intercalated nanocrystallined Mg/Al LDHs (LDH-Cl) were synthesized and used for simultaneous removal of arsenic and natural organic matter (NOM) from contaminated groundwater. Humic acid (HA) was selected as a model compound of NOM. The maximum adsorption capacities of arsenate (As(V)) on LDH-CO3 and LDH-Cl are 44.66 and 88.30 mg/g, respectively, and those of HA on LDH-CO3 and LDH-Cl are 53.16 and 269.24 mg/g, respectively. It was found that more than 98% of arsenic and 94% of NOM were eliminated by LDH-Cl from both arsenic and NOM-rich groundwater, which is used as drinking water in Togtoh County, Inner Mongolia, China. The arsenic concentration declined from 231 to 4 μg/L, which meets the drinking water standard. The adsorption mechanisms were determined by using X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and extended X-ray absorption fine structure spectroscopy techniques (EXAFS). The results showed that the removal of HA was mainly via surface complexation as well as coagulation at the surface of LDHs, while the adsorption of As(V) was mainly via ion-exchange process. The presence of HA exhibited little inhibiting effect on As(V) adsorption by occupying partial binding sites on LDH surfaces. Nevertheless, it could not affect the ion-exchange process of As(V) with the interlayer anions of LDHs. The removal of As(V) and HA can be carried out independently due to the different adsorption mechanisms. By integrating the experimental results, it is clear that LDH-Cl can be potentially used as a cost-effective material for the purification of both arsenic and NOM contaminated groundwater.

Metallic 1T-LixMoS2 Cocatalyst Significantly Enhanced the Photocatalytic H2 Evolution over Cd0.5Zn0.5S Nanocrystals under Visible Light Irradiation

In the present work, metallic 1T-LixMoS2 is utilized as a novel cocatalyst for Cd0.5Zn0.5S photocatalyst. The obtained LixMoS2/Cd0.5Zn0.5S hybrids show excellent photocatalytic performance for H2 generation from aqueous solution containing Na2S and Na2SO3 under splitting visible light illumination (λ ≥ 420 nm) without precious metal cocatalysts. It turns out that a certain amount of intercalating Li(+) ions ultimately drives the transition of MoS2 crystal from semiconductor triagonal phase (2H phase) to metallic phase (1T phase). The distinct properties of 1T-LixMoS2 promote the efficient separation of photoexcited electrons and holes when used as cocatalyst for Cd0.5Zn0.5S photocatalyst. As compared to 2H-MoS2 nanosheets only having edge active sites, photoinduced electrons not only transfer to the edge sites of 1T-LixMoS2, but also to the plane active sites of 1T-LixMoS2 nanosheets. The content of LixMoS2 in hybrid photocatalysts influences the photocatalytic activity. The optimal 1T-LixMoS2 (1.0 wt %)/Cd0.5Zn0.5S nanojunctions display the best activity for hydrogen production, achieving a hydrogen evolution rate of 769.9 μmol h(-1), with no use of noble metal loading, which is about 3.5 times higher than that of sole Cd0.5Zn0.5S, and 2 times higher than that of 2H-MoS2 (1.0 wt %)/Cd0.5Zn0.5S samples. Our results demonstrate that Li(+)-intercalated MoS2 nanosheets with high conductivity, high densities of active sites, low cost, and environmental friendliness are a prominent H2 evolution cocatalyst that might substitute for noble metal for potential hydrogen energy applications.

Large improvement of visible-light photocatalytic H2-evolution based on cocatalyst-free Zn0.5Cd0.5S synthesized through a two-step process

Final metal sulfides Zn0.5Cd0.5S (ZnCdS-CH) are synthesized through a coprecipitation process followed by hydrothermal treatment. The morphological, structural and optical properties have been investigated extensively via diverse analytical techniques. The ZnCdS-CH solid solution without noble metal loading is employed in photocatalytic H2 evolution under visible light irradiation (λ ≥ 420 nm) and achieves a superior activity rate of 0.971 mmol h−1, which exceeds those of coprecipitated Zn0.5Cd0.5S (ZnCdS-C) samples by more than 13 times. Moreover, in the recycle test, the ZnCdS-CH photocatalyst shows a stable photocatalytic activity for H2 evolution under long-term visible-light irradiation. Characterization analyses demonstrate that the excellent photocatalytic H2-evolution performance of the ZnCdS-CH sample arises predominantly from the two-step processing procedure of coprecipitation followed by hydrothermal treatment at 200 °C, which makes it possess a hexagonal (wurtzite) structure, good dispersity, enhanced crystallinity, an appropriate band gap, a more negative conduction band, as well as a large number of surface defect states. This finding is of great significance for designing a facile, reproducible and inexpensive method to realise the potential of ZnxCd1−xS ternary metal sulfides in the field of H2 evolution by water splitting.

Bare Cd1-xZnxS ZB/WZ Heterophase Nanojunctions for Visible Light Photocatalytic Hydrogen Production with High Efficiency.

In this work, we report the synthesis of Cd1-xZnxS zinc blende/wurtzite (ZB/WZ) heterophase nanojunctions with highly efficient charge separation by a solvothermal method in a mixed solution of diethylenetriamine (DETA) and distilled water. l-Cysteine was selected as a sulfur source and a protecting ligand for stabilization of the ZB/WZ homojunction. The optimal ternary chalcogenide Cd0.7Zn0.3S elongated nanocrystals (NCs) without any cocatalyst loading show very high visible light photocatalytic activity with H2 production efficiency of 3.13 mmol h(-1) and an apparent quantum efficiency of 65.7% at 420 nm. This is one of the best visible light photocatalysts ever reported for photocatalytic hydrogen production without any cocatalysts. The charge separation efficiency, having a critical role in enhancing photocatalytic activity for hydrogen production, was significantly improved. Highly efficient charge separation with a prolonged carrier lifetime is driven by the internal electrostatic field originating from the type-II staggered band alignment at the ZB/WZ junctions, as confirmed by steady and time-resolved photoluminescence spectra. Further, the strong binding between the l-cysteine ligand and Cd1-xZnxS elongated nanocrystals protects and stabilizes NCs; the l-cysteine ligand at the interface could trap holes from Cd1-xZnxS NCs, while photogenerated electrons transfer to Cd1-xZnxS catalytic sites for proton reduction. Our results demonstrate that Cd1-xZnxS ZB/WZ heterophase junctions stabilized by l-cysteine molecules can effectively separate charge carriers and achieve highly visible light photocatalytic hydrogen production. The present study provides a new insight into the design and fabrication of advanced materials with homojunction structures for photocatalytic applications and optoelectronic devices.

Self-templated synthesis of novel carbon nanoarchitectures for efficient electrocatalysis

The cost-efficient large-scale production of novel carbon nanostructure with high performance is still a challenge, restricting their applications in catalysis. Herein, we present a low-cost one-pot and one-step approach for the synthesis of both N-doped graphene (NG) and N-doped carbon nanotubes (NCNTs) from self-templated organic nanoplates. By varying the FeCl3 concentration in the precursor, we can control the formation of graphene or CNTs. To the best of our knowledge, this is the first example for the controllable synthesis of graphene or CNTs by varying the precursors’ compositions. This provides a simple and cost-effective route for the large-scale production of both NG and NCNTs for applications in catalysis. By example, we show how these unique structured nanocarbons can be applied in electrocatalysis for oxygen reduction reaction (ORR). The obtained NG and NCNTs show excellent ORR activities with long-term stability under alkaline conditions. The unique porous nanostructure, abundant defects, homogeneous N-doping and high N-content in the NG and NCNTs can provide abundant active sites, leading to the excellent ORR performance. This research not only displayed a simple and cost-effective approach for the large-scale production of novel carbon nanoarchitectures, but also revealed the exceptional application potential of these nanocarbons for electrocatalysis.

Hydrogenation/oxidation triggered highly efficient reversible color switching of organic molecules

Catalytic hydrogenation and oxidative dehydrogenation reactions are fundamental and significant processes in organic transformation, and reversible color switching of organic redox dyes finds potential applications in rewritable paper, sensing devices, data recording and security feature technologies. In this study, we report an interesting result of reversible hydrogenation and oxidative dehydrogenation of a redox dye over a Pd–ZnO1−x hybrid nanocatalyst under ambient conditions. Thionine (TH+) is used as a model compound to evaluate the catalytic performance. The reversible color switching between purple thionine (TH+) and colorless leuco-thionine (LTH) depends on the reducing or oxidizing environments. Our newly developed Pd–ZnO1−x nanocatalyst exhibits high catalytic activity for the hydrogenation of TH+ with a turnover frequency (TOF) as high as 397 h−1 under H2 (1 bar). The oxidative dehydrogenation of LTH is performed under 1 bar O2 flow in the same reaction system. The Pd–ZnO1−x nanocatalyst readily adsorbs and subsequently dissociates O2 to oxidize LTH to the original purple colored TH+ with higher efficiency. The abundant oxygen vacancies on ZnO1−x nanorods and strong metal–support interaction (SMSI) promote the adsorption and subsequent dissociation of molecular hydrogen and oxygen leading to high catalytic activity. This novel reversible color switching of organic dyes can be performed successively for more than 10 cycles in a one pot-fashion using a Pd–ZnO1−x nanocatalyst with a small loss in performance. The highly efficient reversible color switching of TH+/LTH over the Pd–ZnO1−x nanocatalyst provides a state-of-the-art protocol to find practical applications as printing inks for rewritable paper and in sensing and security feature devices.