To couple hydrogen evolution reaction (HER) with urea oxidation reaction (UOR) is a promising approach to produce H2 with reduced energy consumption. However, the development of a low‐cost and ...high‐performance bifunctional electrocatalyst toward HER and UOR is still a challenge. In this work, oxygen‐incorporated nickel molybdenum phosphide nanotube arrays are synthesized on nickel foam (O‐NiMoP/NF) via electrodeposition accompanied with in‐situ template etching. Benefiting from the modulated electronic structure and the nanotube array architecture of O‐NiMoP, the self‐supporting O‐NiMoP/NF electrodes demonstrate highly efficient bifunctional catalytic activity toward HER and UOR. Particularly, in the HER and UOR (HER||UOR) coupled system for H2 production, a significantly reduced cell voltage of 1.55 V is obtained at the current density of 50 mA cm–2, which is about 300 mV lower than that of the conventional water electrolysis. Density functional theory calculations reveal that the remarkable HER and UOR activities originated from the Ni sites with the modulated electronic environment induced by Mo, P and O atoms, which facilitate the water dissociation during HER and balance the adsorption/desorption of the intermediates during UOR. The development of Ni‐based phosphides nanotube arrays as a bifunctional electrocatalyst in HER||OER system provides a new approach enabling energy‐saving H2 production.
Oxygen‐incorporated nickel molybdenum phosphide nanotube arrays supported on nickel foam (O‐NiMoP/NF) for electrocatalytic urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) are synthesized via electrodeposition accompanied with in situ template etching. Benefiting from the nanotube array architecture and the modulated electronic environment of O‐NiMoP, the O‐NiMoP/NF electrodes exhibit efficient bifunctional electrocatalytic activity in the HER||UOR coupled system for H2 production with a low voltage of 1.55 V at 50 mA cm−2.
Conjugated microporous polymers (CMPs) are a unique class of materials that combine extended π-conjugation with a permanently microporous skeleton. Since their discovery in 2007, CMPs have become ...established as an important subclass of porous materials. A wide range of synthetic building blocks and network-forming reactions offers an enormous variety of CMPs with different properties and structures. This has allowed CMPs to be developed for gas adsorption and separations, chemical adsorption and encapsulation, heterogeneous catalysis, photoredox catalysis, light emittance, sensing, energy storage, biological applications, and solar fuels production. Here we review the progress of CMP research since its beginnings and offer an outlook for where these materials might be headed in the future. We also compare the prospect for CMPs against the growing range of conjugated crystalline covalent organic frameworks (COFs).
A novel low‐cost aluminum–graphite dual‐ion battery is reported. The battery shows a reversible capacity of ≈100 mAh g−1 and a capacity retention of 88% after 200 charge–discharge cycles. A packaged ...aluminum–graphite battery is estimated to deliver an energy density of ≈150 Wh kg−1 at a power density of ≈1200 W kg−1, which is ≈50% higher than most commercial lithium ion batteries.
Traditional photosensitizers (PSs) show reduced singlet oxygen (1O2) production and quenched fluorescence upon aggregation in aqueous media, which greatly affect their efficiency in photodynamic ...therapy (PDT). Meanwhile, non‐targeting PSs generally yield low efficiency in antibacterial performance due to their short lifetimes and small effective working radii. Herein, a water‐dispersible membrane anchor (TBD‐anchor) PS with aggregation‐induced emission is designed and synthesized to generate 1O2 on the bacterial membrane. TBD‐anchor showed efficient antibacterial performance towards both Gram‐negative (Escherichia coli) and Gram‐positive bacteria (Staphylococcus aureus). Over 99.8 % killing efficiency was obtained for methicillin‐resistant S. aureus (MRSA) when they were exposed to 0.8 μm of TBD‐anchor at a low white light dose (25 mW cm−2) for 10 minutes. TBD‐anchor thus shows great promise as an effective antimicrobial agent to combat the menace of multidrug‐resistant bacteria.
A membrane‐anchored photosensitizer, termed TBD‐anchor, capable of aggregation‐induced emission, generates 1O2 on the bacterial membrane. Over 99.8 % killing efficiency was obtained for methicillin‐resistant Staphylococcus aureus (MRSA) exposed to 0.8 μm of TBD‐anchor and white‐light irradiation. TBD‐anchor shows great promise as an effective antimicrobial agent for the treatment of antibiotic‐resistant bacterial infections.
Extensive recent progress has been made on the design and applications of organic photothermal agents for biomedical applications because of their excellent biocompatibility comparing with inorganic ...materials. One major hurdle for the further development and applications of organic photothermal agents is the rarity of high‐performance materials in the second near‐infrared (NIR‐II) window, which allows deep tissue penetration and causes minimized side effects. Up till now, there have been few reported NIR‐II‐active photothermal agents and their photothermal conversion efficiencies are relatively low. Herein, optical absorption of π‐conjugated small molecules from the first NIR window to the NIR‐II window is precisely regulated by molecular surgery of substituting an individual atom. With this technique, the first demonstration of a conjugated oligomer (IR‐SS) with an absorption peak beyond 1000 nm is presented, and its nanoparticle achieves a record‐high photothermal conversion efficiency of 77% under 1064 nm excitation. The nanoparticles show a good photoacoustic response, photothermal therapeutic efficacy, and biocompatibility in vitro and in vivo. This work develops a strategy to boost the light‐harvesting efficiency in the NIR‐II window for cancer theranostics, offering an important step forward in advancing the design and application of NIR‐II photothermal agents.
Molecular surgery on π‐conjugated small molecules at the atomic level to tune optical absorption in the second near‐infrared region is reported. With this technique, an absorption peak at 1060 nm is achieved and its nanoparticle shows a record high photothermal conversion efficiency of 77% under 1064 nm excitation, and high performance of in vivo photothermal theranostics is demonstrated.
Owing to the unique advantages of photoacoustic imaging (PAI) and photothermal therapy (PTT) conducted over the near‐infrared‐II (NIR‐II) window, the development of high‐efficiency optical agents ...with NIR‐II light responsiveness is of great significance. Despite the diversity of optical agents developed for NIR‐II PAI and PTT, most of them are based on inorganic nanomaterials and small molecular dyes, whose biosafety and photostability need to be further assessed, respectively. Organic semiconducting macromolecular dyes (OSMDs) featuring a large semiconducting backbone are becoming alternative candidates for NIR‐II PAI and PTT owing to their reliable biocompatibility, durable photostability, and ideal photothermal conversion capability. This paper reviews the current progress of OSMD‐based PAI and PTT in the NIR‐II optical window. The three main types of OSMDs with different skeleton architectures are introduced, and their applications for NIR‐II PAI (tumor imaging, stem cell tracking, and vasculature imaging) and PTT (tumor ablation) are described. Viable strategies for further improving the NIR‐II PAI performance of OSMDs are discussed. Finally, some major issues faced by OSMDs in NIR‐II PAI and PTT are raised, and the future development directions of OSMDs are analyzed.
This review summarizes the recent progress in organic semiconducting macromolecular dyes (OSMDs) for near‐infrared‐II (NIR‐II) photoacoustic imaging (PAI) and photothermal therapy (PTT). The latest strategies to boost the NIR‐II PAI performance of OSMDs are also presented. Furthermore, some pending issues for OSMDs in NIR‐II PAI and PTT are summarized, and the future outlook is discussed.
Aqueous dual‐ion batteries (ADIBs) based on the cooperative redox of cations and iodine anions at the anode and cathode respectively, are attracting increasing interest because of high capacity and ...safety. However, the full‐cell performance is limited by the sluggish iodine redox kinetics between iodide and polyiodide involving multiple electron transfer steps, and the undesirable shuttling effect of polyiodides. Here, this work reports a versatile conjugated microporous polymer functionalized with secondary amine groups as an organocatalytic cathode for ADIB, which can be positively charged and electrostatically adsorb iodide, and organocatalyze iodine redox reactions through the amine groups. Both theoretical calculations and controlled experiments confirm that the secondary amine groups confine (poly)iodide species via hydrogen bonding, which is essential for accelerating iodine redox kinetics and reducing the polyiodide shuttling effect. The ADIB achieves an ultrahigh capacity of 730 mAh g−1 with an ultrasmall overpotential of 47 mV at 1 A g−1, which also exhibits excellent rate performance and long cycling stability with a capacity retention of 74% after 5000 cycles at a high current density of 5 A g−1. This work demonstrates the promise of developing organocatalysts for accelerating electrochemical processes, which remains a virtually unexplored area in electrocatalyst design for clean energy applications.
The organocatalytic mechanism of secondary amine functionalized phenylamine‐based conjugated microporous polymer (PA‐CMP) cathode on iodine redox through H···I bridging is systematically investigated. The I− anion based aqueous dual‐ion battery demonstrates outstanding electrochemical performance with ultrahigh capacity of 730/516 mAh g−1 at 1/15 A g−1, ultralow overpotential of 47/129 mV at 1/15 A g−1, and stable long‐term performance for over 5000 cycles.
Targeting programmed cell death protein 1 (PD‐1)/programmed death ligand 1 (PD‐L1) immunologic checkpoint blockade with monoclonal antibodies has achieved recent clinical success in antitumor ...therapy. However, therapeutic antibodies exhibit several issues such as limited tumor penetration, immunogenicity, and costly production. Here, Bristol‐Myers Squibb nanoparticles (NPs) are prepared using a reprecipitation method. The NPs have advantages including passive targeting, hydrophilic and nontoxic features, and a 100% drug loading rate. BMS‐202 is a small‐molecule inhibitor of the PD‐1/PD‐L1 interaction that is developed by BMS. Transfer of BMS‐202 NPs to 4T1 tumor‐bearing mice results in markedly slower tumor growth to the same degree as treatment with anti‐PD‐L1 monoclonal antibody (α‐PD‐L1). Consistently, the combination of Ce6 NPs with BMS‐202 NPs or α‐PD‐L1 in parallel shows more efficacious antitumor and antimetastatic effects, accompanied by enhanced dendritic cell maturation and infiltration of antigen‐specific T cells into the tumors. Thus, inhibition rates of primary and distant tumors reach >90%. In addition, BMS‐202 NPs are able to attack spreading metastatic lung tumors and offer immune‐memory protection to prevent tumor relapse. These results indicate that BMS‐202 NPs possess effects similar to α‐PD‐L1 in the therapies of 4T1 tumors. Therefore, this work reveals the possibility of replacing the antibody used in immunotherapy for tumors with BMS‐202 NPs.
Photodynamic therapy induces apoptosis and necrosis of 4T1 tumor cells, leading to the release of tumor‐associated antigens. Matured dendritic cells migrate to the lymph node to activate T cells which infiltrate to the tumor cells. Small‐molecule inhibitor BMS‐202 acts through programmed death ligand 1 (PD‐L1) dimerization to block the activity of PD‐L1 proteins thus restoring T cell function.
2D perovskites have emerged as one of the most promising photovoltaic materials owing to their excellent stability compared with their 3D counterparts. However, in typical 2D perovskites, the highly ...conductive inorganic layers are isolated by large organic cations leading to quantum confinement and thus inferior electrical conductivity across layers. To address this issue, the large organic cations are replaced with small propane‐1,3‐diammonium (PDA) cations to reduce distance between the inorganic perovskite layers. As shown by optical characterizations, quantum confinement is no longer dominating in the PDA‐based 2D perovskites. This leads to considerable enhancement of charge transport as confirmed with electrochemical impedance spectroscopy, time‐resolved photoluminescence, and mobility measurements. The improved electric properties of the interlayer‐engineered 2D perovskites yield a power conversion efficiency of 13.0%. Furthermore, environmental stabilities of the PDA‐based 2D perovskites are improved. PDA‐based 2D perovskite solar cells (PSCs) with encapsulation can retain over 90% of their efficiency upon storage for over 1000 h, and PSCs without encapsulation can maintain their initial efficiency at 70 °C for over 100 h, which exhibit promising stabilities. These results reveal excellent optoelectronic properties and intrinsic stabilities of the layered perovskites with reduced interlayer distance.
2D perovskites with reduced interlayer distance are synthesized by using propane‐1,3‐diammonium (PDA). The quantum‐confinement effect that is usually observed in 2D perovskites is minimized in the engineered 2D perovskites, which facilitates charge transport between inorganic layers. With enhanced charge‐transport properties, PDA2MA3Pb4I13 perovskite solar cells yield an efficiency up to 13.0% and exhibit better stability.
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