Rational Design of S-Scheme Heterojunction toward Efficient Photocatalytic Cellulose Reforming for H2 and Formic Acid in Pure Water.

Photocatalytic cellulose reforming usually requires harsh conditions due to its sluggish kinetics. Here, a hollow structural S-scheme heterojunction of ZnSe and oxygen vacancy enriched TiO2 , namely, h-ZnSe/Pt@TiO2 , is designed and fabricated, with which the photocatalytic reforming of cellulose for H2 and formic acid is realized in pure water. H2 and formic acid productivity of 1858 and 372 µmol g-1 h-1 and a steady H2 evolution for 300 h are achieved with α-cellulose. Comparable photocatalytic activity can also be achieved using various cellulose sources. It is experimentally proven that the photogenerated charge transfer follows an S-scheme mechanism, which not only promotes the charge separation but also preserves the higher reductive and oxidative abilities of the ZnSe and TiO2 , respectively. Furthermore, the polyhydroxy species produced during cellulose degradation are favored to adsorb on the oxygen vacancy enriched TiO2 surface, which promotes the photocatalytic reforming process and is accounted to the preservation of formic acid as the major solution-phase product. In addition, sequential reactions of oxidation of aldehydes and elimination of formic acid of the cellulose degradation process are revealed. This work provides a photocatalytic strategy to sustainably produce hydrogen and value-added chemicals from biomass under the most environmentally benign condition, i.e., pure water.

Two-Dimensional Ultrathin Graphic Carbon Nitrides with Extended π-Conjugation as Extraordinary Efficient Hydrogen Evolution Photocatalyst.

Construction of 2D graphic carbon nitrides (g-CNx ) with wide visible light adsorption range and high charge separation efficiency concurrently is of great urgent demand and still very challenging for developing highly efficient photocatalysts for hydrogen evolution. To achieve this goal, a two-step pyrolytic strategy has been applied here to create ultrathin 2D g-CNx with extended the π-conjugation. It is experimentally proven that the extension of π-conjugation in g-CNx is not only beneficial to narrowing the bandgap, but also improving the charge separation efficiency of the g-CNx . As an integral result, extraordinary apparent quantum efficiencies (AQEs) of 57.3% and 7.0% at short (380 nm) and long (520 nm) wavelength, respectively, are achieved. The formation process of the extended π-conjugated structures in the ultrathin 2D g-CNx has been investigated using XRD, FT-IR, Raman, XPS, and EPR. Additionally, it has been illustrated that the two-step pyrolytic strategy is critical for creating ultrathin g-CNx nanosheets with extended π-conjugation by control experiments. This work shows a feasible and effective strategy to simultaneously expand the light adsorption range, enhance charge carrier mobility and depress electron-hole recombination of g-CNx for high-efficient photocatalytic hydrogen evolution.

Tuning the current rectification behavior of Rh2-based molecular junctions by varying their supramolecular structures.

Molecular junctions with similar backbones, tunable chemical structures and controllable length are critical for the systematic study of the structure-functionality relationships of their charge transport behavior. Taking advantage of the feasibility and tunability of stepwise fabrication, we built series of asymmetric supramolecular SAMs on gold using Rh2(O2CCR3)4 (Rh2, R = CH3, H, and F) as the building blocks and conjugated N,N'-bidentate ligands (pyrazine (LS), 4,4'-bipyridine (LM) and 1,2-bis(4-pyridyl)ethene (LL)) as the bridges. By varying the Rh2 units and bridging ligands, series of supramolecules with similar backbone and tunable chemical structures were assembled on gold. Their charge transport behavior was examined using conductive-probe atomic force microscopy. Notably, current rectification diminishes gradually as the degree of conjugation of the bridging ligands gets larger from LS to LL due to the decrease in the energy gap between the donor and the acceptor in π(Rh2)-π(L) conjugated MO arrays. Additionally, current rectification can be enhanced when the charge transport mechanistic transits from tunneling in dimers to hopping in tetramers. Unlike charges hopping along the MO arrays in tetramers, charges tunnel through the frontier MOs in dimers. The occupied frontier MOs of dimers localize near the center of the supramolecules or delocalize on the donor and acceptor, which contributes to the weakening of the asymmetric charge tunneling. This work reveals that the frontier MO configurations of these supramolecules could be adjusted by varying their chemical structures, and consequently realize tuning of their charge transport behavior, which deepens the understanding of the charge transport behavior and benefits the establishment of the structure-functionality relationship of Rh2-based molecular junctions.