Advanced Functional Materials

Weng, Gao; Dong, Zixing; Xiang, Pan; Zhu, Yelin; Wu, Chao; Yang, Xianzhong; Liu, Huakun; Dou, Shixue

doi: 10.1002/adfm.202400839pmid: N/A

By virtue of the intrinsic safety and cost‐effectiveness, aqueous Zn‐ion batteries (AZIBs) have gained increasing attention in the realm of energy storage. In spite of the promise of Zn anode, challenges like dendrite growth and side reactions persist as hurdles to be overcome. Addressing this, the rational design of Zn anode current collectors (ZACCs) is an effective solution. Recent years have witnessed the significant strides in the construction of ZACCs, yet the precise pathways for ZACC development remain unclear, lacking a set of specific criteria to guide progress. In this comprehensive review, acknowledging the concerns surrounding Zn anodes, six criteria—electrical conductivity, zincophilicity, orientational deposition inducibility, chemical stability, mechanical durability, and scalability—are innovatively put forward as pivotal benchmarks for the design of ZACCs. Each criterion is accompanied by tailored optimization strategies and corresponding challenges. Furthermore, future trend in ZACCs development is envisaged, along with potential application scenarios for AZIBs. This review will expedite the advancement of ZACCs and contribute to the flourishing landscape of AZIBs.

Naveed, Ahmad; Ai, Haoqiang; Li, Teng; Ali, Amjad; Moradian, Jamile Mohammadi; Qureshi, Waqar Ahmad; Su, Mingru; Li, Xiaowei; Zhou, Yu; Guo, Ruiqiang; Wan, Tao; Lin, Chun‐Ho; Chu, Dewei; Liu, Yunjian

Chen, Xue; Shi, Lei; Ran, Xiao‐Yun; Xu, Ji‐Xuan; Zhang, Li‐Na; Kong, Qing‐Quan; Yu, Xiao‐Qi; Li, Kun

doi: 10.1002/adfm.202400728pmid: N/A

The efficient generation of reactive oxygen species (ROS) is crucial for the photodynamic therapy (PDT) effect. The D‐π‐A molecular engineering strategy can effectively separate the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) distribution to achieve a smaller energy gap thereby facilitating ROS generation of photosensitizers (PSs). Incorporating heterocycles as π‐bridges can not only extend the conjugation system with improving the degree of π‐delocalization but also effectively accelerate the intersystem crossing process. Herein, a N‐heterocycle purine is innovatively integrated into the D‐π‐A structure as a π‐bridge, which significantly enhances the photodynamic performance by achieving high levels of Type I and Type II ROS generation. The most potent TPM‐QN2 is obtained by modulating the electron‐withdrawing ability of the acceptor (quinolinium), with a 1O2 yield of 9.32, which is the highest yield reported to date. Furthermore, these purine‐based PSs exhibit excellent capabilities in promoting cell photodynamic ablation and inhibiting tumor tissue growth. This novel approach of introducing natural heterocycles provides a promising avenue for developing high‐performance PSs and promoting tumor phototherapy.

Wang, Weiyi; Song, Jun; Yu, Weijie; Chen, Meng; Li, Guangru; Chen, Jinli; Chen, Liang; Yu, Luodan; Chen, Yu

doi: 10.1002/adfm.202400929pmid: N/A

Bacteria‐initiated cancer therapy has been demonstrated high therapeutic efficacy against cancer. However, the undesired therapeutic efficacy and induced systematic inflammation storm compromise the therapeutic effect and outcome. Herein, a thermally‐activated living nanomedicine composed of reactive biohybrid (designated as Sa@FeS) is rationally designed and engineered for enhancing hydrogen sulfide (H2S)‐combined chemodynamic oncotherapy by biomineralizing ferrous sulfide nanoparticles (FeS NPs) onto the surface of a Salmonella typhimurium strain (Sa) without reducing bacterial activity. Ascribed to the deep penetration capability of Sa, FeS NPs facilitate photothermally‐enhanced catalytic Fenton reaction of decomposing endogenous H2O2 into cytotoxic hydroxyl radicals deep in tumor tissues upon near infrared irradiation. Meanwhile, Sa bacteria maintain sustained H2S release within tumor for achieving H2S‐induced intracellular acidosis that favors the generation of reactive oxygen species synergistically. Of note, the thermally‐triggered all‐in‐one strategy effectively inhibits bacterial viability, thus reducing the risk of systematic inflammation storm and ensuring biosafety. Therefore, the engineered nano‐bacteria living system exerts the thermally‐enhanced nanocatalytic and gas therapies to effectively eradicate tumors, providing a distinct paradigm for the combination of synthetic biology and nanomedicine in tumor therapy.

Li, Zhiqiang; Chen, Xing; Yao, Ge; Wei, Lingzhi; Chen, Qianwang; Luo, Qiquan; Zheng, Fangcai; Wang, Hui

doi: 10.1002/adfm.202400859pmid: N/A

The practical application of room‐temperature sodium‐sulfur (RT Na–S) batteries is blocked by the notorious shuttle effect of sodium polysulfides (NaPSs) and sluggish refox reaction kinetics. Single‐atom catalysts (SACs) have been widely studied for boosting the energy storage performance of RT Na‐S batteries. Nevertheless, the catalytic centers of SACs reported so far have focused mainly on symmetrical metal–N4 structures, which offer weak bonding affinity toward polar NaPSs, leading to detrimental shuttle effect and sluggish sulfur conversion kinetics. Herein, a novel asymmetrical Mn–N2 structure is implanted into nitrogen‐doped carbon nanofibers (Mn‐N2/CNs) through thermal NH3 etching of a symmetrical Mn–N2O2 structure. The Mn–N2 structure promotes the bonding affinity and catalytic conversion of NaPSs due to the strengthened d‐p orbital‐hybridization between the d orbital of Mn in the Mn–N2 structure and the p orbital of S in NaPSs. Consequently, Mn‐N2/CNs@S achieves a high capacity of 458 mAh g−1 at 3.0 C with a capacity decay of 0.23% over 2300 cycles. This work offers a promising pathway for regulating the coordination number of SACs with strengthened d‐p orbital‐hybridization for high‐performance RT Na–S batteries.

Zeng, Zhouliangzi; Liu, Zhixiao; Cao, Linlin; Dai, Minyang; Zhang, Wei; Zhang, Yan; Ni, Wenpeng; Zhang, Shiguo

doi: 10.1002/adfm.202400334pmid: N/A

Pervasive intrinsic defects have a significant impact on the electrocatalytic activity of carbon materials, but previous research has focused on the effects of topological structures exclusively. Herein, a compelling demonstration of the pivotal role played by the positions and spatial arrangement of intrinsic defects in determining their efficacy for electrochemical CO2 reduction (ECR) is presented. Theoretical calculations reveal a substantial reduction in energy barriers for *COOH formation at intrinsic defects positioned along the edges while hindering the transformation of *COOH to *CO in the ECR process. To address this issue, a sea urchin‐like nanocarbon (F1100) is designed, which provides adjacent intrinsic defects located in V‐type arranged carbon nanorods. The angulated edge intrinsic defects facilitate the bridge adsorption of carbon monoxide (CO), as confirmed by in situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy, thereby enhancing the specific activity of ECR on intrinsic carbon defects. In a 0.1 m potassium bicarbonate (KHCO3) solution, F1100 achieves a FECO of 95.0%, while in an ionic liquids‐based electrolyte, a current density of 90.0 mA cm−2 is obtained with nearly complete conversion of CO2 to CO in an H‐type cell.

Yang, Yunpeng; Kong, Lingli; Huang, Bai; Lin, Baofeng; Fu, Lihua; Xu, Chuanhui

doi: 10.1002/adfm.202400789pmid: N/A

Real‐time detection of different physiological characteristics is crucial for human physical and mental health. A detection system with multimodal sensing capability, high sensitivity, excellent mechanical properties, and environmental stability is highly desirable, but it is still a great challenge. Inspired by the structural gradient of biological tissues, a multifunctional sensor based on carboxylic styrene butadiene rubber (XSBR) and sodium polyacrylate (PAANa) non‐covalently modified MXenes is prepared in this study, in which the MXenes exhibit a gradient distribution and simultaneously formed an orientation arrangement at the bottom of the matrix through the formation of hydrogen bonding interactions with PAANa. The material shows a considerable stretchability of 244% and strength of 7.67 MPa, high electrical conductivity of 55.40 S m‒1, low percolation threshold of 2.48 wt%, and excellent response to strain (gauge factor of 906.7 within 98% strain) and humidity (relative resistance change of 530% within 11–93% relative humidity). Based on the superior performances of the XSBR/PAANa/MXene composite, an integrated detection system is designed to accurately detect respiration and body movements at various scales. This work provides a new perspective for the development of a novel biomimetic functional material for sensor applications.

Shen, Liu‐Liu; Dong, Xiangzun; Wang, Wei; Yu, Hui; Wu, Peiran; Wang, Jiansong; Xu, Yipu; Cui, Xuanxuan; Li, Xinkun; Zhang, Gui‐Rong; Mei, Donghai

doi: 10.1002/adfm.202400964pmid: N/A

Wood‐derived carbons demonstrate great potential as self‐standing electrodes in energy storage/conversion applications, including supercapacitors and water‐splitting devices. However, the key challenge remains the rational customization of surface functionalities for optimized performance. This study introduces an innovative approach to self‐standing wood‐derived carbons with tailored nitrogen and metal functionalities. In contrast to traditional impregnation techniques, which offer limited precision in surface modification, this approach entails the intentional attachment of amidoxime groups to the wood substrates. These groups serve as nitrogen sources, and create abundant surface anchoring sites for metal ions due to the chelation between the amidoxime groups and metals. The resulting carbons feature uniform and high dispersion of nitrogen and metal functionalities, along with a distinctive hierarchical porosity combining interconnected open channels with abundant mesopores. As a proof‐of‐concept, different metals are incorporated (i.e., Mn, Co, Ni) into the amidoximated‐wood precursors, and the resulting self‐standing carbons showcase excellent performance in both supercapacitors and water‐splitting applications. Leveraging the specific chelating ability of amidoxime groups toward metal ions, this strategy holds great potential as a generic approach to systematically tailoring the surface functionalities of carbon‐based materials for various electrochemical energy storage/conversion processes.

Zhou, Guojun; Wang, Yanting; Mao, Yilin; Guo, Caihong; Zhang, Jian; Molokeev, Maxim S.; Xia, Zhiguo; Zhang, Xian‐Ming

doi: 10.1002/adfm.202401860pmid: N/A

Hybrid metal halides (HMHs) have emerged as a promising platform for optically functional crystalline materials, but it is extremely challenging to thoroughly elucidate the electron transition coupled to additional ligand emission. Herein, to discover sequences of lead‐free HMHs with distinct optically active metal cations are aimed, that is, Sb3+ (5s2) with the lone‐pair electron configuration and In3+ (4d10) with the fully‐filled electron configuration. (Me2NH2)4MCl6·Cl (Me = −CH3, M = Sb, In) exhibits the superior temperature/component‐dependent luminescence behaviors resulting from the competition transition between triplet‐states (Tn‐S0) self‐trapped excitons (STEs) of inorganic units and singlet‐state (S1‐S0) of organic cations, which is manipulated by the optical activity levels of [SbCl6]3− and [InCl6]3−. The bonding differences between Sb3+/In3+ and Cl− in terms of electronic excitation and hybridization are emphasized, and the different electron‐transition mechanisms are established according to the PL spectra at the extreme temperature of 5 to 305 K and theoretical calculations. By fine‐tuning the B‐site Sb3+/In3+ alloying, the photoluminescence quantum yield (PLQY = 81.5%) and stability are optimized at 20% alloying of Sb3+. This research sheds light on the rules governing PL behaviors of HMHs, as well as exploring the optical‐functional application of aviation temperature sensors and access‐control systems.

Liu, Huijing; Xu, Jia; Han, Huifang; Zhao, Chenxu; Fu, Yao; Lang, Kun; Zou, Pengchen; Pan, Xu; Gao, Xingyu; Zhao, Kui; Yao, Jianxi

doi: 10.1002/adfm.202400975pmid: N/A

The mechanical durability and efficiency of all‐inorganic flexible perovskite solar cells (f‐PSCs) still require enhancement for practical applications. In this study, a creative debridement strategy to improve the mechanical durability and photovoltaic performance of all‐inorganic f‐PSCs by pre‐bending the flexible perovskite film and then depositing the passivation agent 2‐mercaptopyridine is proposed. The pre‐bending process induced the generation of microcracks in the perovskite film surface, and 2‐mercaptopyridine can more effectively penetrate the interior of the film through the microcracks, thereby further passivating deep surface defects. These microcracks and defects can be perfectly repaired by 2‐mercaptopyridine. Bidentate coordination sites of S and N in 2‐mercaptopyridine show stronger binding energy with surface defects. The debridement strategy effectively enhanced the crystallization of the film surface and markedly inhibited crack propagation during the film's bending process. The optimized device achieves a champion power conversion efficiency (PCE) of 14.74%. The pre‐bent and passivated all‐inorganic f‐PSC shows 104% of its initial PCE after 15 000 bending cycles at a curvature radius of 3 mm. Remarkably, even after undergoing 70 000 bending cycles at a curvature radius of 5 mm, pre‐bent, and passivated f‐PSC can retain over 93% of its initial PCE, exhibiting excellent mechanical durability.