Synergistic poly(lactic acid) photoreforming and H2 generation over ternary NixCo1-xP/reduced graphene oxide/g-C3N4 composite.

Effective utilization of photoexcited electrons and holes is always a challenge in photocatalytic reactions. Herein, we reported ternary NixCo1-xP/reduced graphene oxide/g-C3N4 (NixCo1-xP/rGO/CN) composite as a photocatalyst for synergistic poly(lactic acid) photoreforming and H2 generation in alkaline aqueous solution. The rate of H2 production over the optimal 15Ni0·1Co0·9P/rGO/CN reached 576.7 µmol h-1 g-1, which is 3.6 times as high as binary 15Ni0·1Co0·9P/CN composite. The apparent quantum efficiency of the optimal 15Ni0·1Co0·9P/rGO/CN was 1.7% at λ = 420 nm monochromatic light. Mott-Schottky analysis suggested that the photogenerated electrons transfer along the pathway of CN→rGO→Ni0·1Co0·9P, where rGO and Ni0·1Co0·9P functioned as the medium for electron transporting and reaction site for H2 generation, respectively. Meanwhile, poly(lactic acid) was photoreformed into formate and acetate by the photogenerated holes and hydroxyl radical. This work demonstrates that ternary NixCo1-xP/rGO/CN composite can be applied as a cheap and promising photocatalyst for synergistic plastic photoreforming and H2 generation.

Numerical algorithms for solving self-consistent field theory reversely for block copolymer systems.

Besides dictating the equilibrium phase diagram, the rugged free-energy landscape of AB block copolymers gives rise to a multitude of non-equilibrium phenomena. Self-consistent field theory (SCFT) can be employed to calculate the mean-field free energy, F [ ϕ A t a r g e t ] , of a non-equilibrium unstable state that is characterized by a given spatial density distribution, ϕ A t a r g e t , in the incompressible system. Such a free-energy functional is the basis of describing the structure formation by dynamic SCFT techniques or the identification of minimum free-energy paths via the string method. The crucial step consists in computing the external potential fields that generate the given density distribution in the corresponding system of non-interacting copolymers, i.e., the potential-to-density relation employed in equilibrium SCFT calculations has to be inverted (reverse SCFT calculation). We describe, generalize, and evaluate the computational efficiency of two different numerical algorithms for this reverse SCFT calculation-the Debye-function algorithm based on the structure factor and the field-theoretic umbrella-potential (FUP) algorithm. In contrast to the Debye-function algorithm, the FUP algorithm only yields the exact mean-field values of the given target densities in the limit of a strong umbrella potential, and we devise a two-step variant of the FUP algorithm that significantly mitigates this issue. For Gaussian copolymers, the Debye-function algorithm is more efficient for highly unstable states that are far away from the equilibrium, whereas the improved FUP algorithm outperforms the Debye-function algorithm closer to metastable states and is easily transferred to more complex molecular architectures.

Process-Accessible States of Block Copolymers.

Process-directed self-assembly of block copolymers refers to thermodynamic processes that reproducibly direct the kinetics of structure formation from a starting, unstable state into a selected, metastable mesostructure. We investigate the kinetics of self-assembly of linear ACB triblock copolymers after a rapid transformation of the middle C block from B to A. This prototypical process (e.g., photochemical transformation) converts the initial, equilibrium mesophase of the ABB copolymer into a well-defined but unstable, starting state of the AAB copolymer. The spontaneous structure formation that ensues from this unstable state becomes trapped in a metastable mesostructure, and we systematically explore which metastable mesostructures can be fabricated by varying the block copolymer composition of the initial and final states. In addition to the equilibrium mesophases of linear AB diblock copolymers, this diagram of process-accessible states includes 7 metastable periodic mesostructures, inter alia, Schoen's F-RD periodic minimal surface. Generally, we observe that the final, metastable mesostructure of the AAB copolymer possesses the same symmetry as the initial, equilibrium mesophase of the ABB copolymer.

Process-directed self-assembly of block copolymers: a computer simulation study.

The free-energy landscape of self-assembling block copolymer systems is characterized by a multitude of metastable minima and concomitant protracted relaxation times of the morphology. Tailoring rapid changes (quench) of thermodynamic conditions, one can reproducibly trap the ensuing kinetics of self-assembly in a specific metastable state. To this end, it is necessary to (1) control the generation of well-defined, highly unstable states and (2) design the unstable state such that the ensuing spontaneous kinetics of structure formation reaches the desired metastable morphology. This process-directed self-assembly provides an alternative to fine-tuning molecular architecture by synthesis or blending, for instance, in order to fabricate complex network structures. Comparing our simulation results to recently developed free-energy techniques, we highlight the importance of non-equilibrium molecular conformations in the starting state and motivate the significance of the local conservation of density.

Directing the self-assembly of block copolymers into a metastable complex network phase via a deep and rapid quench.

The free-energy landscape of self-assembling block copolymer systems is characterized by a multitude of metastable minima. Using particle-based simulations of a soft, coarse-grained model, we explore opportunities to reproducibly direct the spontaneous ordering of these self-assembling systems into a metastable complex network morphology--specifically, Schoen's I-WP periodic minimal surface--starting from a highly unstable state that is generated by a rapid expansion. This process-directed self-assembly provides an alternative to fine-tuning molecular architecture or blending for fabricating complex network structures. Comparing our particle-based simulation results to recently developed free-energy techniques, we critically assess their ability to predict spontaneous formation and highlight the importance of nonequilibrium molecular conformations in the starting state and the local conservation of density.