Search

Spatially confined photocatalysis has emerged as a viable strategy for the intensification of various redox reactions, but the influence of confined structure on reaction behavior is always overlooked in gas‐solid reactions. Herein, we report a nanomembrane with confining Cs3Bi2Br9 nanocrystals inside vertical channels of porous insulated silica thin sheets (CBB@SBA(⊥)) for photocatalytic nitric oxide (NO) abatement. The ordered one‐dimensional (1D) pore channels with mere 70 nm channel length provide a highly accessible confined space for catalytic reactions. A record‐breaking NO conversion efficiency of 98.2 % under a weight hourly space velocity (WHSV) of 3.0×106 mL g−1 h−1, as well as exceptionally high stability over 14 h and durability over a wide humidity range (RH=15–90 %) was realized over SBA(⊥) confined Cs3Bi2Br9, well beyond its nonconfined analogue and the Cs3Bi2Br9 confine in Santa Barbara Amorphous (SBA‐15). Mechanism studies suggested that the insulated pore channels of SBA(⊥) in CBB@SBA(⊥) endow concentrated electron field and enhanced mass transfer that render high exposure of reactive species and lower reaction barrier needs for ⋅O2− formation and NO oxidation, as well as prevents structural degradation of Cs3Bi2Br9. This work expands an innovative strategy for designing efficient photocatalysts for air pollution remediation. [ABSTRACT FROM AUTHOR]

Single‐atom nanozyme (SAzyme) has sparked increasing interest for catalytic antitumor treatment due to their more tunable and diverse active sites than natural metalloenzymes in complex physiological conditions. However, it is usually a hard task to precisely conduct catalysis at tumor sites after intravenous injection of those SAzyme with high reactivity. Moreover, the explorations of SAzymes in the anticancer application are still in its infancy and need to be developed. Herein, an in situ synthesis strategy for Cu SAzyme was constructed to convert adsorbed copper ions into isolated atoms anchored by oxygen atoms (Cu−O2/Cu−O4) via GSH‐responsive deformability of supports. Our results suggest that the in situ activation process could further facilitate the dissociation of copper ions and the consumption of glutathione, thereby leading to copper deposition in cytoplasm and triggering cuproptosis. Moreover, the in situ synthesis of Cu SAzyme with peroxidase‐like activity enabled the intracellular reactive oxygen species production, resulting in specifically disturbance of copper metabolism pathway. Meanwhile, the in situ exposed glucose transporter (GLUT) inhibitor phloretin (Ph) can block the glycose uptake to boost cuproptosis efficacy. Overall, this in situ activation strategy effectively diminished the off‐target effects of SACs‐induced catalytic therapies and introduced a promising treatment paradigm for advancing cuproptosis‐associated therapies. [ABSTRACT FROM AUTHOR]

We herein present an approach of photo‐induced disproportionation for preparation of Type‐I photodynamic agents. As a proof of concept, BODIPY‐based photosensitizers were rationally designed and prepared. The photo‐induced intermolecular electron transfer between homotypic chromophores leads to the disproportionation reaction, resulting in the formation of charged intermediates, cationic and anionic radicals. The cationic radicals efficiently oxidize the cellularimportant coenzyme, tetrahydrobiopterin (BH4), and the anionic radicals transfer electrons to oxygen to produce superoxide radicals (O2−⋅). One of our Type‐I photodynamic agents not only self‐assembles in water but also effectively targets the endoplasmic reticulum. It displayed excellent photocytotoxicity even in highly hypoxic environments (2 % O2), with a half‐maximal inhibitory concentration (IC50) of 0.96 μM, and demonstrated outstanding antitumor efficacy in murine models bearing HeLa tumors. [ABSTRACT FROM AUTHOR]

With the rapid development of external minimally invasive or noninvasive therapeutic modalities, ultrasound‐based sonodynamic therapy (SDT) is a new alternative for treating deep tumors. However, inadequate sonosensitizer efficiency and poor biosecurity limit clinical applications. In this study, we prepared an oxygen‐vacancy‐engineered W18O49−x nanobrush with a band gap of 2.79 eV for highly efficient SDT using a simple solvothermal method. The suitable band structures of the W18O49−x nanobrush endows it with the potential to simultaneously produce singlet oxygen (1O2), superoxide anions (⋅O2−), and hydroxyl radicals (⋅OH) under ultrasound irradiation. Additionally, abundant oxygen vacancies that serve as further charge traps that inhibit electron‐hole recombination are incidentally introduced through one‐step thermal reduction. Collectively, the in vitro and in vivo results demonstrate that the oxygen‐vacancy‐engineered W18O49−x nanobrush delivers highly efficient reactive oxygen species (ROS) for SDT in a very biosafe manner. Overall, this study provides a new avenue for discovering and designing inorganic nanosonosensitizers with enhanced therapeutic efficiencies for use in SDT. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P−O)δ− modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P−O)δ− has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P−O)δ− modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P−O)δ− modified oxide‐derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm−2 and a cathodic potential of −1.2 V vs. RHE in an alkaline electrolyte. [ABSTRACT FROM AUTHOR]

Sonodynamic therapy (SDT) has garnered growing interest owing to its high tissue penetration depth and minimal side effects. However, the lack of efficient sonosensitizers remains the primary limiting factor for the clinical application of this treatment method. Here, defect‐repaired graphene phase carbon nitride (g‐C3N4) nanosheets are prepared and utilized for enhanced SDT in anti‐tumor treatment. After defect engineering optimization, the bulk defects of g‐C3N4 are significantly reduced, resulting in higher crystallinity and exhibiting a polyheptazine imide (PHI) structure. Due to the more extended conjugated structure of PHI, facilitating faster charge transfer on the surface, it exhibits superior SDT performance for inducing apoptosis in tumor cells. This work focuses on introducing a novel carbon nitride nanomaterial as a sonosensitizer and a strategy for optimizing sonosensitizer performance by reducing bulk defects. [ABSTRACT FROM AUTHOR]

High‐performing n‐type polymers are crucial for the advance of organic electronics field, however strong electron‐deficient building blocks with optimized physicochemical properties for constructing them are still limited. The imide‐functionalized polycyclic aromatic hydrocarbons (PAHs) with extended π‐conjugated framework, high electron deficiency and good solubility serve as promising candidates for developing high‐performance n‐type polymers. Among the PAHs, phenanthrene (PhA) features a well‐delocalized aromatic π‐system with multiple modifiable active sites. However, the PhA‐based imides are seldom studied, mainly attributed to the synthetic challenge. Herein, we report two functionalized PhAs, CPOI and CPCNI, by simultaneously incorporating imide with carbonyl or dicyanomethylene onto PhA. Notably, the dicyanomethylene‐modified CPCNI exhibits a well stabilized LUMO energy level (−3.84 eV), attributed to the synergetic inductive effect from imide and cyano groups. Subsequently, based on CPOI and CPCNI, two polymers PCPOI‐Tz and PCPCNI‐Tz were developed. Applied to organic thin‐film transistors, owing to the strong electron‐deficiency of CPCNI, polymer PCPCNI‐Tz shows an improved electron mobility and largely decreased threshold voltage compared with PCPOI‐Tz. This work affords two structurally novel electron‐deficient building blocks and highlights the effectiveness of dual functionalization of PhAs with strong electron‐withdrawing groups for devising n‐type polymers. [ABSTRACT FROM AUTHOR]

Nanoconfined polymer molecules exhibit profound transformations in their properties and behaviors. Here, we present the synthesis of a polymer‐in‐MOF single ion conducting solid polymer electrolyte, where polymer segments are partially confined within nanopores ZIF‐8 particles through Lewis acid‐base interactions for solid‐state sodium‐metal batteries (SSMBs). The unique nanoconfinement effectively weakens Na ion coordination with the anions, facilitating the Na ion dissociation from salt. Simultaneously, the well‐defined nanopores within ZIF‐8 particles provide oriented and ordered migration channels for Na migration. As a result, this pioneering design allows the solid polymer electrolyte to achieve a Na ion transference number of 0.87, Na ion conductivity of 4.01×10−4 S cm−1, and an extended electrochemical voltage window up to 4.89 V vs. Na/Na+. The assembled SSMBs (with Na3V2(PO4)3 as the cathode) exhibit dendrite‐free Na‐metal deposition, promising rate capability, and stable cycling performance with 96 % capacity retention over 300 cycles. This innovative polymer‐in‐MOF design offers a compelling strategy for advancing high‐performance and safe solid‐state metal battery technologies. [ABSTRACT FROM AUTHOR]

Glycerol is a byproduct of biodiesel production. Selective photoelectrochemical oxidation of glycerol to high value‐added chemicals offers an economical and sustainable approach to transform renewable feedstock as well as store green energy at the same time. In this work, we synthesized monoclinic WO3 nanosheets with exposed (002) facets, which could selectively oxidize glycerol to glyceric acid (GLYA) with a photocurrent density of 1.7 mA cm−2, a 73 % GLYA selectivity and a 39 % GLYA Faradaic efficiency at 0.9 V vs. reversible hydrogen electrode (RHE) under AM 1.5G illumination (100 mW cm−2). Compared to (200) facets exposed WO3, a combination of experiments and theoretical calculations indicates that the superior performance of selective glycerol oxidation mainly originates from the better charge separation and prolonged carrier lifetime resulted from the plenty of surface trapping states, lower energy barrier of the glycerol‐to‐GLYA reaction pathway, more abundant active sites and stronger oxidative ability of photogenerated holes on the (002) facets exposed WO3. Our findings show great potential to significantly contribute to the sustainable and environmentally friendly chemical processes via designing high performance photoelectrochemical cell via facet engineering for renewable feedstock transformation. [ABSTRACT FROM AUTHOR]

Developing low‐cost and high‐performance n‐type polymer semiconductors is essential to accelerate the application of organic thermoelectrics (OTEs). To achieve this objective, it is critical to design strong electron‐deficient building blocks with simple structure and easy synthesis, which are essential for the development of n‐type polymer semiconductors. Herein, we synthesized two cyano‐functionalized highly electron‐deficient building blocks, namely 3,6‐dibromopyrazine‐2‐carbonitrile (CNPz) and 3,6‐Dibromopyrazine‐2,5‐dicarbonitrile (DCNPz), which feature simple structures and facile synthesis. CNPz and DCNPz can be obtained via only one‐step reaction and three‐step reactions from cheap raw materials, respectively. Based on CNPz and DCNPz, two acceptor–acceptor (A–A) polymers, P(DPP‐CNPz) and P(DPP‐DCNPz) are successfully developed, featuring deep‐positioned lowest unoccupied molecular orbital (LUMO) energy levels, which are beneficial to n‐type organic thin‐film transistors (OTFTs) and OTEs performance. An optimal unipolar electron mobility of 0.85 and 1.85 cm2 V−1 s−1 is obtained for P(DPP‐CNPz) and P(DPP‐DCNPz), respectively. When doped with N‐DMBI, P(DPP‐CNPz) and P(DPP‐DCNPz) show high n‐type electrical conductivities/power factors of 25.3 S cm−1/41.4 μW m−1 K−2, and 33.9 S cm−1/30.4 μW m−1 K−2, respectively. Hence, the cyano‐functionalized pyrazine CNPz and DCNPz represent a new class of structurally simple, low‐cost and readily accessible electron‐deficient building block for constructing n‐type polymer semiconductors. [ABSTRACT FROM AUTHOR]