Molecular and Heterojunction Device Engineering of Solution-Processed Conjugated Reticular Oligomers: Enhanced Photoelectrochemical Hydrogen Evolution through High-Effective Exciton Separation.

Covalent organic frameworks (COFs) face limited processability challenges as photoelectrodes in photoelectrochemical water reduction. Herein, sub-10 nm benzothiazole-based colloidal conjugated reticular oligomers (CROs) are synthesized using an aqueous nanoreactor approach, and the end-capping molecular strategy to engineer electron-deficient units onto the periphery of a CRO nanocrystalline lattices (named CROs-Cg). This results in stable and processable "electronic inks" for flexible photoelectrodes. CRO-BtzTp-Cg and CRO-TtzTp-Cg expand the absorption spectrum into the infrared region and improve fluorescence lifetimes. Heterojunction device engineering is used to develop interlayer heterojunction and bulk heterojunction (BHJ) photoelectrodes with a hole transport layer, electron transport layer, and the main active layers, using a CROs/CROs-Cg or one-dimensional (1D) electron-donating polymer HP18 mixed solution via spinning coating. The ITO/CuI/CRO-TtzTp-Cg-HP18/SnO2/Pt photoelectrode shows a photocurrent of 94.9 µA cm‒2 at 0.4 V versus reversible hydrogen electrode (RHE), which is 47.5 times higher than that of ITO/Bulk-TtzTp. Density functional theory calculations show reduced energy barriers for generating adsorbed H* intermediates and increased electron affinity in CROs-Cg. Mott-Schottky and charge density difference analyses indicate enhanced charge carrier densities and accelerated charge transfer kinetics in BHJ devices. This study lays the groundwork for large-scale production of COF nanomembranes and heterojunction structures, offering the potential for cost-effective, printable energy systems.

All-Covalent Organic Framework Nanofilms Assembled Lithium-Ion Capacitor to Solve the Imbalanced Charge Storage Kinetics.

Free-standing covalent organic framework (COFs) nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li+ in lithium-ion batteries, while simultaneously exposing affluent active sites in supercapacitors. The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors (LICs). Herein, for the first time, custom-made COFBTMB-TP and COFTAPB-BPY nanofilms are synthesized as the anode and cathode, respectively, for an all-COF nanofilm-structured LIC. The COFBTMB-TP nanofilm with strong electronegative-CF3 groups enables tuning the partial electron cloud density for Li+ migration to ensure the rapid anode kinetic process. The thickness-regulated cathodic COFTAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity. Due to the aligned 1D channel, 2D aromatic skeleton and accessible active sites of COF nanofilms, the whole COFTAPB-BPY//COFBTMB-TP LIC demonstrates a high energy density of 318 mWh cm-3 at a high-power density of 6 W cm-3, excellent rate capability, good cycle stability with the capacity retention rate of 77% after 5000-cycle. The COFTAPB-BPY//COFBTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors. After being comprehensively explored via ex situ XPS, 7Li solid-state NMR analyses, and DFT calculation, it is found that the COFBTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C-F bonds during lithium storage. COFBTMB-TP exhibits a strong interaction with Li+ due to the C-F, C=O, and C-N bonds, facilitating Li+ desolation and absorption from the electrolyte. This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.

Covalent Organic Framework Fiber-Constructed Artificial Solid Electrolyte Interphase Layer: Facilitated Uniform Deposition of Li+ and Encapsulated Li Dendrite.

Due to ultrahigh theoretical capacity and ultralow redox poteneial, lithium metal is considered as a promising anode material. However, uneven lithium deposition, uncontrollable lithium dendrite formation, and fragile solid electrolyte interphase (SEI) lead to low lithium utilization, rapid capacity decay, and poor cycle performance. Herein, a robust artificial SEI film by coating the lithium surface with fibrous covalent organic framework (Fib-COF) was constructed, which effectively prevented dendrite penetration and battery short-circuits. Experimental results demonstrated that the Fib-COF-decorated batteries showcased higher Coulombic efficiency (CE), extended cycling stability, and superior electrolyte compatibility. The strong affinity of the carbonyl group in Fib-COF towards Li+ contributes to facilitating the Li+ uniform transfer and nucleation. In situ optical microscopy dynamically revealed the formation process of dendrite-free interphase under the function of Fib-COF layer. As a result, the modified Li anode demonstrated remarkable cycle stability for more than 650 h at 20 mA cm-2 and 5 mAh cm-2 in ether-based electrolyte and 1000 h at 0.5 mA cm-2 and 0.5 mAh cm-2 in carbonate-based electrolyte. The dendrite-free Fib-COF@Li electrodes endowed higher specific capacities of 650 mAh g-1 for Fib-COF@Li|S full cell after 250 cycles and 120 mAh g-1 for Fib-COF @Li|LiFePO4 full cells after 300 cycles.

Bending Resistance Covalent Organic Framework Superlattice: "Nano-Hourglass"-Induced Charge Accumulation for Flexible In-Plane Micro-Supercapacitors.

Covalent organic framework (COF) film with highly exposed active sites is considered as the promising flexible self-supported electrode for in-plane micro-supercapacitor (MSC). Superlattice configuration assembled alternately by different nanofilms based on van der Waals force can integrate the advantages of each isolated layer to exhibit unexpected performances as MSC film electrodes, which may be a novel option to ensure energy output. Herein, a mesoporous free-standing A-COF nanofilm (pore size is 3.9 nm, averaged thickness is 4.1 nm) with imine bond linkage and a microporous B-COF nanofilm (pore size is 1.5 nm, averaged thickness is 9.3 nm) with ß-keto-enamine-linkages are prepared, and for the first time, we assembly the two lattice matching films into sandwich-type superlattices via layer-by-layer transfer, in which ABA-COF superlattice stacking into a "nano-hourglass" steric configuration that can accelerate the dynamic charge transportation/accumulation and promote the sufficient redox reactions to energy storage. The fabricated flexible MSC-ABA-COF exhibits the highest intrinsic CV of 927.9 F cm-3 at 10 mV s-1 than reported two-dimensional alloy, graphite-like carbon and undoped COF-based MSC devices so far, and shows a bending-resistant energy density of 63.2 mWh cm-3 even after high-angle and repeat arbitrary bending from 0 to 180°. This work provides a feasible way to meet the demand for future miniaturization and wearable electronics.

Modulating the Band Structure of Metal Coordinated Salen COFs and an In Situ Constructed Charge Transfer Heterostructure for Electrocatalysis Hydrogen Evolution.

A series of crystalline, stable Metal (Metal = Zn, Cu, Ni, Co, Fe, and Mn)-Salen covalent organic framework (COF)EDA complex are prepared to continuously tune the band structure of Metal-Salen COFEDA , with the purpose of optimizing the free energy intermediate species during the hydrogen evolution reaction (HER) process. The conductive macromolecular poly(3,4-ethylenedioxythiophene) (PEDOT) is subsequently integrated into the one-dimensional (1D) channel arrays of Metal-Salen COFEDA to form heterostructure PEDOT@Metal-Salen COFEDA via the in situ solid-state polymerization method. Among the Metal-Salen COFEDA and PEDOT@Metal-Salen COFEDA complexes, the optimized PEDOT@Mn-Salen COFEDA displays prominent electrochemical activity with an overpotential of 150 mV and a Tafel slope of 43 mV dec-1 . The experimental results and density of states data show that the continuous energy band structure modulation in Metal-Salen COFEDA has the ability to make the metal d-orbital interact better with the s-orbital of H, which is conducive to electron transport in the HER process. Moreover, the calculated charge density difference indicates that the heterostructures composed of PEDOT and Metal-Salen COFEDA induce an intramolecular charge transfer and construct highly active interfacial sites.

Partially delocalized charge in crystalline Co-S-Se/NiOx nanocomposites for boosting electrocatalytic oxygen evolution.

Although reasonably specified and adjustable preparation of nanostructures with specific morphologies, ordered chemical compositions and electronic structures involving advanced energy chemistries is an important research area, high-efficiency, stable, and low-cost electrocatalysts for water splitting are greatly desirable and challenging. In this study, partially delocalized Co-S-Se ultra-thin nanosheets are obtained via a liquid-liquid interface-mediated strategy at an oil-water interface. These Co-S-Se ultra-thin nanosheets exhibit different-sized lamellar structures and have an average thickness of 0.83 nm. The ternary ultra-thin Co0.45S0.38Se0.17 nanosheets demonstrate excellent performance for the OER, accompanied by an overpotential of 290 mV (1.52 V vs. RHE) at 10 mA cm-2, and a Tafel slope of 74.5 mV dec-1. In the meantime, the catalyst recombined with a stoichiometry NiOx catalyst to form a composite interface, which also exhibited a good OER performance, with an overpotential of 260 mV at 10 mA cm-2 and a smaller Tafel slope of 53.9 mV dec-1. The nanosheets can rearrange the electronic density near the metal catalytic centers and increase the electron transfer. DFT calculations indicate that the partially delocalized charges can improve electrocatalytic performances, demonstrating modulated electroreduction properties. Due to the special atomic and electronic structure of the ternary transition metal alloy chalcogenide, the compound has great potential for energy storage, which will help in the rational design and synthesis of high-efficiency electrocatalysts.

Rational design of covalent triazine frameworks based on pore size and heteroatomic toward high performance supercapacitors.

A series of covalent triazine frameworks (CTFs) are prepared via ionothermal synthesis for supercapacitors. Due to the feature of adjustable pore structure and rich nitrogen, CTFs with regular structure can be used as a group of model compounds to further investigate the influence of pore size and heteroatom on supercapacitors. By comparing the performance of CTFs with different pore structures and nitrogen contents, the experimental results show that BPY-CTF with high specific surface area of 2278 m2 g-1, mesopores structure, and suitable nitrogen content displays a specific capacitance of 393.6 F g-1 at 0.5 A g-1. According to the results and analysis, the existence of mesopores largely enhance the contact area between the electrode material and electrolyte, and then boost the charge transfer. On the other hand, N-doping has a prominent effect on improving the Faradaic pseudo-capacitance and conductivity for CTF electrode materials. This work will inspire further research on the development of highly efficient electrode materials for energy storage devices.

Synergistic Catalysis of Ionic Liquid-Decorated Covalent Organic Frameworks with Polyoxometalates for CO2 Cycloaddition Reaction under Mild Conditions.

The cycloaddition of carbon dioxide (CO2) with epoxides to yield highly value-added cyclic carbonates is an effective way to chemically utilize and convert CO2. Here, a heterogeneous catalyst of imidazole ionic liquid-decorated covalent organic framework with polyoxometalates (POM@ImTD-COF) was constructed by the covalent modification of ionic liquids to COFs and the electrostatic interaction between POMs and ionic liquids. The obtained POM@ImTD-COF shows high catalytic activity for CO2 cycloaddition reaction under mild conditions (1 atm and 80 °C) in the presence of a co-catalyst, and the catalytic activity of POM@ImTD-COF has no obvious decrease during reusing five times. The excellent catalytic performance is mainly attributed to the synergistic effect of ionic liquids, POMs, and COFs. In the cycloaddition process, ionic liquids and the co-catalyst weaken the C-O bond of epoxides and promote the ring opening of epoxides. POMs as the Lewis acids facilitate the insertion of CO2 to form reaction intermediates. The multiple activation effect of ionic liquids and POMs together with the CO2 adsorption effect and well-dispersed active sites in COFs contribute to the remarkable catalytic performance.

Electrochemical Delamination of Ultralarge Few-Layer Black Phosphorus with a Hydrogen-Free Intercalation Mechanism.

Due to strong interlayer interaction and ease of oxidation issues of black phosphorus (BP), the domain size of artificial synthesized few-layer black phosphorus (FL-BP) crystals is often below 10 µm, which extremely limits its further applications in large-area thin-film devices and integrated circuits. Herein, a hydrogen-free electrochemical delamination strategy through weak Lewis acid intercalation enabled exfoliation is developed to produce ultralarge FL-BP single-crystalline domains with high quality. The interaction between the weak Lewis acid tetra-n-butylammonium acetate (CH3 COOTBA) and P atoms promotes the average domain size of FL-BP crystal up to 77.6 ± 15.0 µm and the largest domain size is found to be as large as 119 µm. The presence of H+ and H2 O is found to sharply decrease the size of as-exfoliated FL-BP flakes. The electronic transport measurements show that the delaminated FL-BP crystals exhibit a high hole mobility of 76 cm2 V-1 s-1 and an on/off ratio of 103 at 298 K. A broadband photoresponse from 532 to 1850 nm with ultrahigh responsivity is achieved. This work provides a scalable, simple, and low-cost approach for large-area BP films that meet industrial requirements for nanodevices applications.

Aggregation Tuning with Heavily Fluorinated Donor Polymer for Efficient Organic Solar Cells.

The fluorination/sulfofication-induced effect in the photovoltaic polymer solar cells (PSCs) needs to be paid much attention. In this work, a new donor polymer PBDB-PS2F was synthesized by heavily fluorinated and decorated S atom on the side chain of benzo[1,2-b:4,5-b']dithiophene (BDT) unit to explore the internal combined effect of F&S on the photoelectric performance. It was found that the heavy fluorination on the side chain could make PBDB-PS2F achieve a low highest occupied molecule orbital (HOMO) energy level of -5.72 eV and weaken the torsion of the main chain and effectively increase the intermolecular π-π* transition. Encouragingly, compared with the counterpart polymer PBDB-PS without the fluorination, PBDB-PS2F exhibited a much intense aggregation at room temperature but showed a tendency of reduced aggregation at high temperatures. This feature gives excellent solution processability and uniform morphology in the active layer of a PBDB-PS2F-based device, enabling an outstanding photovoltaic performance with the power conversion efficiency (PCE) of 13.56% (VOC = 0.90 V, JSC = 21.53 mA/cm2, FF = 69.68%). Compared with that of the counterpart polymer PBDB-PS with no heavy fluorination, the VOC of PBDB-PS2F increased by 15.4% and the PCE increased by 30.9%. Thus, the heavy-fluorination-induced effect to construct photovoltaic polymers could be used to improve the performance of polymer solar cells.

Chiral mesoporous silica synthesized by a facile strategy for loading and releasing poorly water-soluble drug.

Most of the mesoporous chiral mesoporous silica (CMS) was synthesized by the chiral surfactant-directing method. In this study, a facile method was designed to synthesize CMS. In this method, achiral amphiphile was used as templating agents, and dilute ammonia solution was applied to induce the chirality of the CMS. Meanwhile, its morphology can be controlled by changing the concentration of the aqueous ammonia solution. The obtained CMS was characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The results showed that all of the CMS possessed highly ordered mesostructures, and as the concentration of ammonia decreases, the chirality of the CMS becomes more obvious. Water-insoluble drug curcumin (Cur) was used as a model drug. The characteristics of CMS before and after drug loading were further detected by Fourier transform infrared spectrometer (FT-IR), N2 adsorption-desorption and differential scanning calorimetry (DSC). The result showed that Cur was successfully loaded inside the pores of the CMS and remained an amorphous state due to steric inhibition. Additionally, CMS could significantly increase the release rate of Cur under different pH conditions.

Size Effect of Two-Dimensional Conjugated Space in Photovoltaic Polymers' Side Chain: Balancing Phase Separation and Charge Transport.

Various two-dimensional (2D) side-chain-substituted benzo(1,2-b:4,5-b')dithiophene (BDT) blocks have been used to construct donor polymers, whereas the size effect of the side chains on the photovoltaic performance was overlooked in the past few years. In this work, three size-varied conjugated spaces (benzene, naphthalene, and biphenyl) were introduced into the corresponding polymers PBDB-Ph, PBDB-Na, and PBDB-BPh. This space engineering has a significant impact on the extent of phase separation in the active layer which blended with the polymer and the acceptor ITCPTC and preserved the desired morphology. The varied space size in the side chains lead to distinct balance mobility ratios of holes to electrons (benzene, 0.21; naphthalene, 0.75; and biphenyl, 0.57). Finally, PBDB-Na-based polymer solar cells (PSCs) delivered the highest power conversion efficiency of 12.52% when compared to the PSC performances of PBDB-Ph (8.48%) and PBDB-BPh (11.35%). The method in tailoring the side chain structures could fabricate a balance between phase separation and charge transport, providing an enlightenment for the development of photovoltaic devices.

Rational Design of Low Band Gap Polymers for Efficient Solar Cells with High Open-Circuit Voltage: The Profound Effect of Me and Cl Substituents with a Similar van Der Waals Radius.

Generally, low band gap material-based photovoltaic devices have reduced open circuit voltage (VOC), and realizing the trade-off between the low band gap (Eg < 1.6 eV) and high VOC (>0.9 V) could be critical to give efficient polymer solar cells, especially for high-performance semitransparent PSCs and tandem solar cells. Although lots of efforts have been made to address the issue, most results have not been gratifying. In this work, the polymer PTBTz-Cl based on the chlorination method and efficient thiazole-induced strategy was designed and synthesized, aiming at the deep HOMO energy level, and the enhanced backbone planarity caused by the weak noncovalent Cl···S interaction. In addition, the methyl-substituted polymer PTBTz-Me was constructed as the reference due to the similar van der Waals radius of the side chain (CH3: 0.20 nm vs Cl: 0.18 nm). Encouragingly, in comparison with that of PTBTz-2, the newly synthesized polymers exhibit the red-shifted absorption spectra ranging from 300 to 770 nm, with an obviously reduced Eg of ∼1.6 eV. However, the function of Cl and Me substituents is different. Compared to the polymer PTBTz-Me, PTBTz-Cl exhibits a lower HOMO value, stronger crystallinity, and more compact intramolecular interactions. Consequently, the polymer PTBTz-Cl exhibits excellent photovoltaic performance with a notable VOC of 0.94 V and a power conversion efficiency of 10.35%, which is ∼11% higher than the 9.12% efficiency based on PTBTz-Me, and is also one of the highest values among polymer/fullerene solar cells. Moreover, a smaller photo energy loss (Eloss) of 0.64 eV is achieved, which is rare among the current high-performance polymer systems.

Pore Surface Engineering of Covalent Triazine Frameworks@MoS2 Electrocatalyst for the Hydrogen Evolution Reaction.

Electrochemical water splitting is an important strategy for the mass production of hydrogen. Development of synthesizable catalysts has always been one of the biggest obstacles to replace platinum-group catalysts. In this work, a high quality crystal polymer covalent triazine framework [CTF; Brunauer-Emmett-Teller (BET) surface area of 1562.6 m2 g-1 ] is synthesized and MoS2 nanoparticles are grown in situ into/onto the 1 D channel arrays or the external surface for electrocatalysis [hydrogen evolution reaction (HER)] . The state-of-the-art CTFs@MoS2 structure exhibits superior catalytic kinetics with an overpotential of 93 mV and Tafel slope of 43 mV dec-1 , which is improved over most other reported analogous catalysts. The inherent π-conjugated crystal channels in CTFs provides a multifunctional support for electron transmission and mass diffusion during the hydrogen evolution process. Catalytic kinetics analysis shows that the HER performance is closely correlated to the hierarchical pore parameters and aggregated thickness of MoS2 nanoparticles. This work provides an attractive and durable alternative to synthesize high activity and stable catalysts for HER.

Tailoring the structures and photonic properties of low-dimensional organic materials by crystal engineering.

Low-dimensional organic materials have given rise to tremendous interest in optoelectronic applications, owing to their controllable photonic properties. However, the controlled-synthesis approaches for organic nano-/micro-architectures are very difficult to attain, because the weak interaction (van der Waals force) between the organic molecules cannot dominate the kinetic process of crystal growth. We report a simple method, which involves selective adhesion to the organic crystal plane by hydrogen-bonding interaction for modulating the crystal growth process, which leads either to the self-assembly of one organic molecule into two-dimensional (2D) microsheets with an obvious asymmetric light propagation or one-dimensional (1D) microrods with low propagation loss. The method of tailoring the structures and photonic properties for fabricating different micro-structures would provide enlightenment for the development of tailor-made mini-sized devices for photonic integrated circuits.

Controlled Synthesis of ZrS2 Monolayer and Few Layers on Hexagonal Boron Nitride.

Group IVB transition metal (Zr and Hf) dichalcogenide (TMD) monolayers can have higher carrier mobility and higher tunneling current density than group VIB (Mo and W) TMD monolayers. Here we report the synthesis of hexagonal ZrS2 monolayer and few layers on hexagonal boron nitride (BN) using ZrCl4 and S as precursors. The domain size of ZrS2 hexagons is around 1-3 µm. The number of layers of ZrS2 was controlled by tuning the evaporation temperature of ZrCl4. The stacking angle between ZrS2 and BN characterized by transmission electron microscopy shows a preferred stacking angle of near 0°. Field-effect transistors (FETs) fabricated on ZrS2 flakes showed n-type transport behavior with an estimated mobility of 0.1-1.1 cm(2) V(-1) s(-1).

New benzo[1,2-b:4,5-b']dithiophene-based small molecules containing alkoxyphenyl side chains for high efficiency solution-processed organic solar cells.

A new acceptor-donor-acceptor (A-D-A) small molecule, namely, BDT-PO-DPP, based on the alkoxyphenyl (PO)-substituted benzo[1,2-b:4,5-b']dithiophene (BDT) derivative and the diketopyrrolopyrrole (DPP) unit was synthesized as an electron donor for solution-processed small-molecule organic solar cells (SMOSCs). BDT-PO-DPP exhibited good thermal stability, with a 5 % weight-lost temperature at 401 °C under a nitrogen atmosphere. BDT-PO-DPP exhibited a lower HOMO energy level of -5.25 eV and a weaker aggregation ability than alkoxy-substituted BDT-O-DPP. A bulk heterojunction SMOSC device based on BDT-PO-DPP and [6,6]-phenyl-C61 -butyric acid methyl ester was prepared, and it showed a power conversion efficiency up to 5.63% with a high open-circuit voltage of 0.83 V, a short circuit current density of 11.23 mA cm(-2) , and a fill factor of 60.37% by using 1,2-dichlorobenzene as the co-solvent after thermal annealing at 110 °C. The results indicate that the alkoxyphenyl-substituted BDT derivative is a promising electron-donor building block for constructing highly efficient solution-processed SMOSCs.

Development of new two-dimensional small molecules based on benzodifuran for efficient organic solar cells.

A new organic small molecule, DCA3TBDF, with a 2D benzo[1,2-b:4,5-b']difuran (BDF) moiety as the central core and octyl cyanoacetate units as the end-capped blocks, was designed and synthesized for solution-processed bulk heterojunction solar cells. DCA3TBDF possesses good solubility in common organic solvents such as toluene, CH2Cl2, chlorobenzene, and CHCl3 and good thermal stability with an onset decomposition temperature with 5% weight-loss occurring at 361 °C. The DCA3TBDF thin film showed a broad absorption at λ=320-700 nm and high crystallinity. Small-molecule organic solar cells based on DCA3TBDF and [6,6]-phenyl-C61-butyric acid methyl ester demonstrated promising power conversion efficiency with a high fill factor under the illumination of AM 1.5G (100 mW cm(-2)).

Synthesis and characterization of functional thienyl-phosphine microporous polymers for carbon dioxide capture.

A novel kind of functional organic microporous polymer is designed by introducing polar organic groups (P=O and P=S) and electron-rich heterocyclic into the framework to obtain high carbon dioxide capture capacity. The estimated Brunauer-Emmett-Teller (BET) surface areas of these polymers are about 600 m(2) g(-1) and the highest CO2 uptake is 2.26 mmol g(-1) (1.0 bar/273 K). Interestingly, the polymer containing P=O groups shows greater CO2 capture capacity than that containing P=S groups at the same temperature. In addition, these polymers show high isosteric heats of CO2 adsorption (28.6 kJ mol(-1) ), which can be competitive with some nitrogen-rich networks. Therefore, these microporous polymers are promising candidates for carbon dioxide capture.