Chenzhe Li

Synthesis of BiVO4@C Core–Shell Structure on Reduced Graphene Oxide with Enhanced Visible‐Light Photocatalytic Activity

Herein, a facile strategy for the controllable synthesis of BiVO4@C core-shell nanoparticles on reduced graphene oxide (RGO) is reported. The BiVO4 particle size can be controlled in the process by adjusting the volume ratio of glycerol in the sol-gel solution. The glycerol layers adsorbed on BiVO4 (BiVO4@glycerol) made it possible to form hydrogen bonds between BiVO4@glycerol and graphene oxide with the assistance of ultrasound. After thermal treatment, glycerol adsorbed on the BiVO4 particles formed amorphous carbon shells to link the particles and RGO. As a result, the obtained RGO-BiVO4@C nanocomposite showed a five times higher rate in O2 evolution from water under visible-light irradiation. Also, it demonstrated a six times higher photocatalytic performance enhancement than that of pure BiVO4 in the degradation of Rhodamine B. The enhanced performance is attributed to the carbon shells that restrict the growth of BiVO4 , the reduced graphene oxide that improves the electronic conductivity of the composite, and importantly, the bonds formed between the carbon shells and RGO that reduce the recombination loss of photogenerated charges effectively. The strategy is simple, effective, and can be extended to other ternary oxides with controlled size and high performance.

Thermal stability of mullite RMn2O5 (R = Bi, Y, Pr, Sm or Gd): Combined density functional theory and experimental study

Understanding and effectively predicting the thermal stability of ternary transition metal oxides with heavy elements using first principle simulations are vital for understanding performance of advanced materials. In this work, we have investigated the thermal stability of mullite RMn2O5 (R  =  Bi, Pr, Sm, or Gd) structures by constructing temperature phase diagrams using an efficient mixed generalized gradient approximation (GGA) and the GGA  +  U method. Simulation predicted stability regions without corrections on heavy elements show a 4-200 K underestimation compared to our experimental results. We have found the number of d/f electrons in the heavy elements shows a linear relationship with the prediction deviation. Further correction on the strongly correlated electrons in heavy elements could significantly reduce the prediction deviations. Our corrected simulation results demonstrate that further correction of R-site elements in RMn2O5 could effectively reduce the underestimation of the density functional theory-predicted decomposition temperature to within 30 K. Therefore, it could produce an accurate thermal stability prediction for complex ternary transition metal oxide compounds with heavy elements.

Soft tendril-inspired grippers: shape-morphing of programmable polymer-paper bilayer composites

Nastic movements in plants that occur in response to environmental stimuli have inspired many man-made shape-morphing systems. Tendril is an exemplification serving as a parasitic grasping component for the climbing plants by transforming from a straight shape into a coiled configuration via the asymmetric contraction of internal stratiform plant tissues. Inspired by tendrils, this study using a three-dimensional (3D) printing approach developed a class of soft grippers with preprogrammed deformations being capable of imitating the general motions of plant tendrils, including bending, spiral, and helical distortions for grasping. These grippers initially in flat configurations were tailored from a polymer-paper bilayer composite sheet fabricated via 3D printing a polymer on the paper substrate with different patterns. The rough and porous paper surface provides a printed polymer that is well-adhered to the paper substrate which in turn serves as a passive strain-limiting layer. During printing, the melted polymer filament is stretched, enabling the internal strain to be stored in the printed polymer as memory, and then it can be thermally released, which will be concurrently resisted by the paper layer, resulting in various transformations based on the different printed geometries. These obtained transformations were then used for designing grippers to grasp objects with corresponding motions. Furthermore, a fully equipped robotic tendril with three segments was reproduced, where one segment was used for grasping the object and the other two segments were used for forming a tendril-like twistless spring-like structure. This study further helps in the development of soft robots using active polymer materials for engineered systems.

Effect of R-site element on crystalline phase and thermal stability of Fe substituted Mn mullite-type oxides: R2(Mn1−xFex)4O10−δ (R = Y, Sm or Bi; x = 0, 0.5, 1)

Combining experimental and theoretical studies, we investigate the role of R-site (R = Y, Sm, Bi) element on the phase formation and thermal stability of R2(Mn1−xFex)4O10−δ (x = 0, 0.5, 1) mullite-type oxides. Our results show a distinct R-site dependent phase behavior for mullite-type oxides as Fe is substituted for Mn: 100% mullite-type phase was formed in (Y, Sm, Bi)2Mn4O10; 55% and 18% of (Y, Sm)2Mn2Fe2O10−δ was found when R = Y and Sm, respectively, for equal Fe and Mn molar concentrations in the reactants, whereas Bi formed 54% O10- and 42% O9-mixed mullite-type phases. Furthermore, when the reactants contain 100% Fe, no mullite-type phase was formed for R = Y and Sm, but a sub-group transition to Bi2Fe4O9 O9-phase was found for R = Bi. Thermogravimetric analysis and density functional theory (DFT) calculation results show a decreasing thermal stability in O10-type structure with increasing Fe incorporation; for example, the decomposition temperature is 1142 K for Bi2Mn2Fe2O10−δ vs. 1217 K for Bi2Mn4O10. On the other hand, Bi2Fe4O9 O9-type structure is found to be thermally stable up to 1227 K. These findings are explained by electronic structure calculations: (1) as Fe concentration increases, Jahn–Teller distortion results in mid band-gap empty states from unstable Fe4+ occupied octahedra, which is responsible for the decrease in O10 structure stability; (2) the directional sp orbital hybridization unique to Bi effectively stabilizes the mullite-type structure as Fe replaces Mn.