Wenfeng Shangguan

Visible-Light Responsive Photocatalytic Fuel Cell Based on WO3/W Photoanode and Cu2O/Cu Photocathode for Simultaneous Wastewater Treatment and Electricity Generation

A visible-light driven photocatalytic fuel cell (PFC) system comprised of WO(3)/W photoanode and Cu(2)O/Cu photocathode was established for organic compounds degradation with simultaneous electricity generation. The central idea for its operation is the mismatched Fermi levels between the two photoelectrodes. Under light illumination, the Fermi level of WO(3)/W photoanode is higher than that of Cu(2)O/Cu photocathode. An interior bias can be produced based on which the electrons of WO(3)/W photoanode can transfer from the external circuit to combine with the holes of Cu(2)O/Cu photocathode then generates the electricity. In this manner, the electron/hole pairs separations at two photoelectrodes are facilitated to release the holes of WO(3)/W photoanode and electrons of Cu(2)O/Cu photocathode. Organic compounds can be decomposed by the holes of WO(3)/W photoanode due to its high oxidation power (+3.1-3.2 V(NHE)). The results demonstrated that various model compounds including phenol, Rhodamine B, and Congo red can be successfully decomposed in this PFC system, with the degradation rate after 5 h operation were obtained to be 58%, 63%, and 74%, respectively. The consistent operation for continuous water treatment with the electricity generation at a long time scale was also confirmed from the result. The proposed PFC system provides a self-sustained and energy-saving way for simultaneous wastewater treatment and energy recovery.

Self-Biasing Photoelectrochemical Cell for Spontaneous Overall Water Splitting under Visible-Light Illumination

A self-biasing photoelectrochemical (PEC) cell that could work for spontaneous overall water splitting in a neutral solution was established based on the mismatched Fermi levels between the photoelectrodes. A Pt-catalyst-decorated crystalline silicon photovoltaic cell (Pt/PVC) was prepared and employed as an effective photocathode. This was coupled with a poly(ethylene glycol)-directed WO3/W photoanode prepared by a hydrothermal process. Both of the photoelectrodes showed a response to visible light. The WO3/W photoanode had a positively located valence band edge, the energy level of which was enough for water oxidation, and the Pt/PVC photocathode possessed a negatively located conduction band edge, which was capable of water reduction. More importantly, the Fermi level of the WO3/W photoanode was more positive than that of the Pt/PVC photocathode because of the p-n junction of the PVC that decoupled the band bending and enlarged the photovoltage. Under visible-light irradiation, the WO3/W photoanode provided a negative bias for the Pt/PVC photocathode, and the Pt/PVC photocathode provided a positive bias for the WO3/W photoanode. An interior bias was generated that could relax the strict criteria of overall water splitting by cooperatively separating the hole-electron pairs at both photoelectrodes. In this system, the short-circuit current and the open-circuit voltage increased with increasing light intensity (AM 1.5 illumination) to reach 121 μA cm(-2) and 0.541 V, respectively, at a light intensity of 100 mW cm(-2). Such a combination provides a promising method for the fabrication of self-driven devices for solar-energy storage.

Unusual catalytic effect of the two-dimensional molecular space with regular triphenylphosphine groups.

A novel organic-inorganic hybrid 2D molecular space with regular triphenylphosphine groups (triphenylphosphineamidephenylsilica, PPh(3)APhS) was successfully synthesized through grafting triphenylphosphine groups in the 2D structure of layered aminophenylsilica dodecyl sulfate (APhTMS-DS), which was developed in our previous research, with regular ammonium groups. The 2D structures were kept after the grafting reaction of triphenylphosphine groups in PPh(3)APhS. The catalytic potentials of 2D molecular space with regular triphenylphosphine groups were investigated. An unusual catalytic effect was found in a carbon-phosphorus ylide reaction. The PPh(3)-catalyzed reaction of modified allylic compounds, including bromides and chlorides with tropone yielded a [3 + 6] annulation product. However, an unusual [8 + 3] cycloadduct was obtained in the reaction of modified allylic compounds, including bromides and chlorides with tropone catalyzed by PPh(3)APhS. Otherwise, the stable catalytic intermediate was successfully separated, and the reaction activity of the catalytic intermediate was confirmed in the reaction of modified allylic compounds with tropone catalyzed by PPh(3)APhS. This research is the first successful example of directly influencing catalytic reaction processes and product structures by utilizing the chemical and geometrical limits of 2D molecular spaces with regular catalyst molecules and affords a novel method for controlling catalytic reaction processes and catalyst design.

Chiral layered molecular spaces with amino acids

Novel chiral layered molecular space L-(+)-leucine amidepropylamidephenylsilica (L-(+)-Leu-APAPhS) and D-(−)-alanine amidepropylamidephenylsilica (D-(−)-Ala-APAPhS) were synthesized through grafting L-leucine tert-butyl ester (L-Leu-OtBu) and D-alanine tert-butyl ester (D-Ala-OtBu), in layered carboxylpropylamidephenylsilica (CPAPhS), which was developed in our previous research, with regular carboxyl groups, and the tert-butyl ester as protective groups of carboxyls in amino acids was cleaved with dilute trifluoroacetic acid (TFA). The improved XRD response indicated that the two dimensional layered structure had been retained in L-Leu-APAPhS and D-Ala-APAPhS. The chiral behaviors of layered molecular spaces CPAPhS, L-(+)-Leu-APAPhS and D-(−)-Ala-APAPhS were investigated. DL-Alanine tert-butyl ester (DL-Ala-OtBu) was grafted in the achiral layered molecular space CPAPhS as enantiomer pair, even if 70% L-Ala-OtBu and 30% D-Ala-OtBu existed in the reaction solution. L-(+)-Leu-APAPhS and D-(−)-Ala-APAPhS represented better chiral selectivity for amino acids both in chiral selective reactions and chiral column chromatography experiments, and exhibited the potential of chiral layered molecular space with an amino acid structure for chiral molecular recognition and selection processes. The formation of L-Leu-APAPhS-L-Ala-OMe also exhibited potential for that multi-amino acid (peptide) can be grafted in CPAPhS to form layered molecular spaces with peptides.

Investigation of catalytic characterization of two-dimensional molecular space with regular ammonium and pyridine groups.

Novel two-dimensional molecular space with regular pyridine groups layered pyridine-4-amidepropylsilica (PAPS) and pyridine-4-amidephenylsilica (PAPhS) were successfully synthesized through grafting pyridine groups in the layer structure of two-dimensional molecular space with regular ammonium groups layered aminopropylsilica (ATMS-DS) and layered aminophenylsilica (APhTMS-DS). The two-dimensional structures were kept after grafting reaction of pyridine groups in PAPS and PAPhS. The catalytic potentials of two-dimensional molecular space with regular ammonium and pyridine groups were investigated. The catalytic capability of APhTMS-DS, PAPS, and PAPhS was confirmed through Knoevenagel condensation reactions. Knoevenagel condensation of aromatic aldehydes with malononitrile was not observed in the presence of ATMS-DS. Otherwise, the lower yield of Knoevenagel condensation of higher active 2-chlorobenzaldehyde with malononitrile in the presence of APhTMS-DS, PAPS, and PAPhS indicated the potential of the two-dimensional molecular space with regular catalyst molecules on influencing catalysis processes utilizing the chemical and geometrical limits.