Sequential closed-loop Bayesian optimization as a guide for organic molecular metallophotocatalyst formulation discovery.

Conjugated organic photoredox catalysts (OPCs) can promote a wide range of chemical transformations. It is challenging to predict the catalytic activities of OPCs from first principles, either by expert knowledge or by using a priori calculations, as catalyst activity depends on a complex range of interrelated properties. Organic photocatalysts and other catalyst systems have often been discovered by a mixture of design and trial and error. Here we report a two-step data-driven approach to the targeted synthesis of OPCs and the subsequent reaction optimization for metallophotocatalysis, demonstrated for decarboxylative sp3-sp2 cross-coupling of amino acids with aryl halides. Our approach uses a Bayesian optimization strategy coupled with encoding of key physical properties using molecular descriptors to identify promising OPCs from a virtual library of 560 candidate molecules. This led to OPC formulations that are competitive with iridium catalysts by exploring just 2.4% of the available catalyst formulation space (107 of 4,500 possible reaction conditions).

Machine Learning Accelerated Exploration of Ternary Organic Heterojunction Photocatalysts for Sacrificial Hydrogen Evolution.

Donor-acceptor heterojunctions in organic photocatalysts can provide enhanced exciton dissociation and charge separation, thereby improving the photocatalytic activity. However, the wide choice of possible donors and acceptors poses a challenge for the rational design of organic heterojunction photocatalysts, particularly for large ternary phase spaces. We accelerated the exploration of ternary organic heterojunction photocatalysts (TOHP) by using a combination of machine learning and high-throughput experimental screening. This involved 736 experiments in all, out of possible 4320 ternary combinations. The top ten most active TOHPs discovered using this strategy showed outstanding sacrificial hydrogen production rates of more than 500 mmol g-1 h-1, with the most active ternary material reaching a rate of 749.8 mmol g-1 h-1 under 1 sun illumination. These rates of photocatalytic hydrogen generation are among the highest reported for organic photocatalysts in the literature.

Packing-induced selectivity switching in molecular nanoparticle photocatalysts for hydrogen and hydrogen peroxide production.

Molecular packing controls optoelectronic properties in organic molecular nanomaterials. Here we report a donor-acceptor organic molecule (2,6-bis(4-cyanophenyl)-4-(9-phenyl-9H-carbazol-3-yl)pyridine-3,5-dicarbonitrile) that exhibits two aggregate states in aqueous dispersions: amorphous nanospheres and ordered nanofibres with π-π molecular stacking. The nanofibres promote sacrificial photocatalytic H2 production (31.85 mmol g-1 h-1) while the nanospheres produce hydrogen peroxide (H2O2) (3.20 mmol g-1 h-1 in the presence of O2). This is the first example of an organic photocatalyst that can be directed to produce these two different solar fuels simply by changing the molecular packing. These different packings affect energy band levels, the extent of excited state delocalization, the excited state dynamics, charge transfer to O2 and the light absorption profile. We use a combination of structural and photophysical measurements to understand how this influences photocatalytic selectivity. This illustrates the potential to achieve multiple photocatalytic functionalities with a single organic molecule by engineering nanomorphology and solid-state packing.

A Pyrene-4,5,9,10-Tetraone-Based Covalent Organic Framework Delivers High Specific Capacity as a Li-Ion Positive Electrode.

Electrochemically active covalent organic frameworks (COFs) are promising electrode materials for Li-ion batteries. However, improving the specific capacities of COF-based electrodes requires materials with increased conductivity and a higher concentration of redox-active groups. Here, we designed a series of pyrene-4,5,9,10-tetraone COF (PT-COF) and carbon nanotube (CNT) composites (denoted as PT-COFX, where X = 10, 30, and 50 wt % of CNT) to address these challenges. Among the composites, PT-COF50 achieved a capacity of up to 280 mAh g-1 as normalized to the active COF material at a current density of 200 mA g-1, which is the highest capacity reported for a COF-based composite cathode electrode to date. Furthermore, PT-COF50 exhibited excellent rate performance, delivering a capacity of 229 mAh g-1 at 5000 mA g-1 (18.5C). Using operando Raman microscopy the reversible transformation of the redox-active carbonyl groups of PT-COF was determined, which rationalizes an overall 4 e-/4 Li+ redox process per pyrene-4,5,9,10-tetraone unit, accounting for its superior performance as a Li-ion battery electrode.

Reconstructed covalent organic frameworks.

Covalent organic frameworks (COFs) are distinguished from other organic polymers by their crystallinity1-3, but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions are poorly reversible4,5. More reversible chemistry can improve crystallinity6-9, but this typically yields COFs with poor physicochemical stability and limited application scope5. Here we report a general and scalable protocol to prepare robust, highly crystalline imine COFs, based on an unexpected framework reconstruction. In contrast to standard approaches in which monomers are initially randomly aligned, our method involves the pre-organization of monomers using a reversible and removable covalent tether, followed by confined polymerization. This reconstruction route produces reconstructed COFs with greatly enhanced crystallinity and much higher porosity by means of a simple vacuum-free synthetic procedure. The increased crystallinity in the reconstructed COFs improves charge carrier transport, leading to sacrificial photocatalytic hydrogen evolution rates of up to 27.98 mmol h-1 g-1. This nanoconfinement-assisted reconstruction strategy is a step towards programming function in organic materials through atomistic structural control.

Photocatalytic Overall Water Splitting Under Visible Light Enabled by a Particulate Conjugated Polymer Loaded with Palladium and Iridium.

Polymer photocatalysts have received growing attention in recent years for photocatalytic hydrogen production from water. Most studies report hydrogen production with sacrificial electron donors, which is unsuitable for large-scale hydrogen energy production. Here we show that the palladium/iridium oxide-loaded homopolymer of dibenzo[b,d]thiophene sulfone (P10) facilitates overall water splitting to produce stoichiometric amounts of H2 and O2 for an extended period (>60 hours) after the system stabilized. These results demonstrate that conjugated polymers can act as single component photocatalytic systems for overall water splitting when loaded with suitable co-catalysts, albeit currently with low activities. Transient spectroscopy shows that the IrO2 co-catalyst plays an important role in the generation of the charge separated state required for water splitting, with evidence for fast hole transfer to the co-catalyst.

3 × 40 Gbit/s All-Optical Logic Operation Based on Low-Loss Triple-Mode Silicon Waveguide.

Information capacity of single-mode fiber communication systems face fundamental limitations imposed by optical nonlinearities. Spatial division multiplexing (SDM) offers a new dimension for upgrading fiber communication systems. Many enabling integrated devices, such as mode multiplexers and multimode bending with low crosstalk, have been developed. On the other hand, all-optical signal processing (AOSP) can avoid optical to electrical to optical (O-E-O) conversion, which may potentially allow for a low cost and green operation for large-scale signal processing applications. In this paper, we show that the system performance of AOSP can be pushed further by benefiting from the existing technologies developed in spatial mode multiplexing (SDM). By identifying key technologies to balance the impacts from mode-dependent loss, crosstalk and nonlinearities, three-channel 40 Gbit/s optical logic operations are demonstrated using the first three spatial modes in a single multimode waveguide. The fabricated device has a broadband four-wave mixing operation bandwidth (>20 nm) as well as high conversion efficiency (>-20 dB) for all spatial modes, showing the potential for a large-scale signal processing capacity with the combination of wavelength division multiplexing (WDM) and SDM in the future.

Linear Conjugated Polymers for Solar-Driven Hydrogen Peroxide Production: The Importance of Catalyst Stability.

Hydrogen peroxide (H2O2) is one of the most important industrial oxidants. In principle, photocatalytic H2O2 synthesis from oxygen and H2O using sunlight could provide a cleaner alternative route to the current anthraquinone process. Recently, conjugated organic materials have been studied as photocatalysts for solar fuels synthesis because they offer synthetic tunability over a large chemical space. Here, we used high-throughput experiments to discover a linear conjugated polymer, poly(3-4-ethynylphenyl)ethynyl)pyridine (DE7), which exhibits efficient photocatalytic H2O2 production from H2O and O2 under visible light illumination for periods of up to 10 h or so. The apparent quantum yield was 8.7% at 420 nm. Mechanistic investigations showed that the H2O2 was produced via the photoinduced stepwise reduction of O2. At longer photolysis times, however, this catalyst decomposed, suggesting a need to focus the photostability of organic photocatalysts, as well as the initial catalytic production rates.

Optically Reconfigurable Spin-Valley Hall Effect of Light in Coupled Nonlinear Ring Resonator Lattice.

Scattering immune propagation of light in topological photonic systems may revolutionize the design of integrated photonic circuits for information processing and communications. In optics, various photonic topological circuits have been developed, which were based on classical emulation of either quantum spin Hall effect or quantum valley Hall effect. On the other hand, the combination of both the valley and spin degrees of freedom can lead to a new kind of topological transport phenomenon, dubbed spin-valley Hall effect (SVHE), which can further expand the number of topologically protected edge channels and would be useful for information multiplexing. However, it is challenging to realize SVHE in most known material platforms, due to the requirement of breaking both the (pseudo)fermionic time-reversal (T) and parity symmetries (P) individually, but leaving the combined symmetry S≡TP intact. Here, we propose an experimentally feasible platform to realize SVHE for light, based on coupled ring resonators mediated by optical Kerr nonlinearity. Thanks to the inherent flexibility of cross-mode modulation, the coupling between the probe light can be engineered in a controllable way such that spin-dependent staggered sublattice potential emerges in the effective Hamiltonian. With delicate yet experimentally feasible pump conditions, we show the existence of spin-valley Hall-induced topological edge states. We further demonstrate that both degrees of freedom, i.e., spin and valley, can be manipulated simultaneously in a reconfigurable manner to realize spin-valley photonics, doubling the degrees of freedom for enhancing the information capacity in optical communication systems.

Nano-assemblies of a soluble conjugated organic polymer and an inorganic semiconductor for sacrificial photocatalytic hydrogen production from water.

Nanostructured materials have interesting optical and electronic properties that are often drastically different from those of their bulk counterparts. While bulk organic/inorganic semiconductor composites have attracted much attention in the past decade, the preparation of organic/inorganic semiconductor nanocomposites (OISNs) still remains challenging. This work presents an assembly method for the co-encapsulation of titanium dioxide dots (TDs) with a cyano-substituted soluble conjugated polymer (CSCP) into a particular nanoparticle. The as-prepared CSCP/TD semiconductor nanocomposites (CSCP/TD NCs) exhibit different particle surfaces and morphologies depending on the mass ratio of the CSCP to TDs. We then tested them as photocatalysts for sacrificial hydrogen production from water. We found that nanocomposites outperformed nanoparticles of the individual components and physical mixtures thereof. The most active CSCP/TD NC had a catalytic H2 production rate that was 4.25 times higher than that of pure polymer nanoparticles prepared under the same conditions. We ascribe this to energy transfer between the semiconductors, where direct phase contact is essential, highlighting a potential avenue for using soluble, visible light-absorbing conjugated organic polymers to build Z-schemes for overall water splitting in the future.

Crosslinked Polyimide and Reduced Graphene Oxide Composites as Long Cycle Life Positive Electrode for Lithium-Ion Cells.

Conjugated polymers with electrochemically active redox groups are a promising class of positive electrode material for lithium-ion batteries. However, most polymers, such as polyimides, possess low intrinsic conductivity, which results in low utilization of redox-active sites during charge cycling and, consequently, poor electrochemical performance. Here, it was shown that this limitation can be overcome by synthesizing polyimide composites (PIX) with reduced graphene oxide (rGO) using an in situ polycondensation reaction. The polyimide composites showed increased charge-transfer performance and much larger specific capacities, with PI50, which contains 50 wt % of rGO, showing the largest specific capacity of 172 mAh g-1 at 500 mA g-1 . This corresponds to a high utilization of the redox active sites in the active polyimide (86 %), and this composite retained 80 % of its initial capacity (125 mAh g-1 ) after 9000 cycles at 2000 mA g-1 .

Synthesis of Stable Thiazole-Linked Covalent Organic Frameworks via a Multicomponent Reaction.

The development of robust synthetic routes to stable covalent organic frameworks (COFs) is important to broaden the range of applications for these materials. We report here a simple and efficient three-component assembly reaction between readily available aldehydes, amines, and elemental sulfur via a C-H functionalization and oxidative annulation under transition-metal-free conditions. Five thiazole-linked COFs (TZ-COFs) were synthesized using this method. These materials showed high levels of crystallinity, high specific surface areas, and excellent physicochemical stability. The photocatalytic applications of TZ-COFs were investigated, and TZ-COF-4 gave high sacrificial hydrogen evolution rates from water (up to 4296 µmol h-1 g-1 under visible light irradiation) coupled with high stability and recyclability, with sustained hydrogen evolution for 50 h.

Conjugated polymer donor-molecular acceptor nanohybrids for photocatalytic hydrogen evolution.

A library of 237 organic binary/ternary nanohybrids consisting of conjugated polymers donors and either fullerene or non-fullerene molecular acceptors was prepared and screened for sacrificial photocatalytic hydrogen evolution activity. PCDTBT/PC60BM nanohybrid showed a high hydrogen evolution rate of 105.2 mmol g-1 h-1 under visible light (λ > 420 nm).

On the Hamiltonian form of cross-mode modulation in nonlinear optical waveguides.

It is commonly believed that the Hamiltonian approach applies only to linear systems, or nonlinear systems with proper linearization procedures. In this Letter, we show that the Hamiltonian approach based on linear coupled-mode theory applies very well for cross-mode modulation, i.e., field variation of the probe light induced by a strong co-propagating pump light in a degenerate mode group. By deriving eigenvalues and eigenvectors of the nonlinear system, evolution of the probe light can be obtained, which agrees with numerical simulations of multimode nonlinear Schrödinger equations. Using the Hamiltonian approach, a simple approach for determining the pump mode for realizing arbitrary mode conversion is discussed. Two concrete scenarios of the optically induced vector mode conversions within the LP11-mode group are further exemplified.

Time-domain characteristics of ultrafast transverse mode switching based on Si nanowires.

We investigate the potential of an ultrafast transverse mode switch based on silicon on insulator (SOI) platform for the switching applications in the spatial division multiplexing (SDM) systems. The impact of waveguide geometry, operation wavelength, pulse width of the pump and probe waves, as well as the temporal delay between the pulses are discussed with a special focus on the temporal switching windows of the switch. The optimized switching performances are further applied to a switching node in a hybrid optical time division-multiplexing (OTDM) and SDM system. The switching energy of the Si-based switch is shown to be potentially smaller than that of the Si3N4 based integration platform.

Optimized Structure of the Traffic Flow Forecasting Model With a Deep Learning Approach.

Forecasting accuracy is an important issue for successful intelligent traffic management, especially in the domain of traffic efficiency and congestion reduction. The dawning of the big data era brings opportunities to greatly improve prediction accuracy. In this paper, we propose a novel model, stacked autoencoder Levenberg-Marquardt model, which is a type of deep architecture of neural network approach aiming to improve forecasting accuracy. The proposed model is designed using the Taguchi method to develop an optimized structure and to learn traffic flow features through layer-by-layer feature granulation with a greedy layerwise unsupervised learning algorithm. It is applied to real-world data collected from the M6 freeway in the U.K. and is compared with three existing traffic predictors. To the best of our knowledge, this is the first time that an optimized structure of the traffic flow forecasting model with a deep learning approach is presented. The evaluation results demonstrate that the proposed model with an optimized structure has superior performance in traffic flow forecasting.