Pub Date : 2025-08-04DOI: 10.26599/nr.2025.94907879
Miao Yu, Qiao Ye, Feng Wang, Abdukader Abdukayum, Nianpeng Li, Lei Zhang, Chuan Zuo, Weiping Liu, Xue Zhao, Guangzhi Hu
Hydrogen production by electrolysis of water is a key technology to achieve green hydrogen energy economy, but it relies on advanced catalyst materials with high efficiency, stability and wide pH adaptability. In this study, Ni, Ru and Pt ternary metals were embedded into nitrogen-doped hollow carbon spheres by hydrothermal tandem heat treatment to form ternary supported metal nanoparticles with high dispersion and ultra-small particle size (~1.3 nm), which realized efficient hydrogen evolution from multi-scenario electrocatalytic water splitting. In the whole pH range, the performance of NiRuPt/NHCSs is better than that of commercial Pt/C catalyst, and the overpotentials under alkaline, neutral and acidic conditions are as low as 15.5, 20.0, and 29.5 mV, respectively. Under industrial conditions, NiRuPt/NHCSs also have excellent HER performance, achieving efficient electrolysis of seawater for hydrogen production, and achieving ampere-level hydrogen production at low voltage (~1.76 V) on integrated membrane electrode assemblies. Density functional theory (DFT) calculations show that in the NiRuPt ternary metal, the Pt site is conducive to promoting the desorption of *H to form H2, the Ru site is conducive to promoting the capture of H2O, and the Ni site is conducive to promoting the dissociation of H2O. Therefore, the formed NiRuPt ternary metal synergistically promotes multi-scenario efficient electrolysis of water to produce hydrogen. This study provides a new idea for the design of multi-component metal/carbon-based composite catalysts, and promotes the development of non-noble metal/noble metal composite catalysts in hydrogen production by electrolysis of water.
{"title":"Ternary metal NiRuPt partition synergistic relay promotes pH-universal hydrogen evolution","authors":"Miao Yu, Qiao Ye, Feng Wang, Abdukader Abdukayum, Nianpeng Li, Lei Zhang, Chuan Zuo, Weiping Liu, Xue Zhao, Guangzhi Hu","doi":"10.26599/nr.2025.94907879","DOIUrl":"https://doi.org/10.26599/nr.2025.94907879","url":null,"abstract":"Hydrogen production by electrolysis of water is a key technology to achieve green hydrogen energy economy, but it relies on advanced catalyst materials with high efficiency, stability and wide pH adaptability. In this study, Ni, Ru and Pt ternary metals were embedded into nitrogen-doped hollow carbon spheres by hydrothermal tandem heat treatment to form ternary supported metal nanoparticles with high dispersion and ultra-small particle size (~1.3 nm), which realized efficient hydrogen evolution from multi-scenario electrocatalytic water splitting. In the whole pH range, the performance of NiRuPt/NHCSs is better than that of commercial Pt/C catalyst, and the overpotentials under alkaline, neutral and acidic conditions are as low as 15.5, 20.0, and 29.5 mV, respectively. Under industrial conditions, NiRuPt/NHCSs also have excellent HER performance, achieving efficient electrolysis of seawater for hydrogen production, and achieving ampere-level hydrogen production at low voltage (~1.76 V) on integrated membrane electrode assemblies. Density functional theory (DFT) calculations show that in the NiRuPt ternary metal, the Pt site is conducive to promoting the desorption of *H to form H<sub>2</sub>, the Ru site is conducive to promoting the capture of H<sub>2</sub>O, and the Ni site is conducive to promoting the dissociation of H<sub>2</sub>O. Therefore, the formed NiRuPt ternary metal synergistically promotes multi-scenario efficient electrolysis of water to produce hydrogen. This study provides a new idea for the design of multi-component metal/carbon-based composite catalysts, and promotes the development of non-noble metal/noble metal composite catalysts in hydrogen production by electrolysis of water.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"19 1","pages":"94907879-94907879"},"PeriodicalIF":0.0,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sciopen.com/article_pdf/1952260535191379970.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-04DOI: 10.26599/nr.2025.94907875
Yue Long, Jie Ling, Wenqian Wei, Yi Lv, Xiaoling Guo, Yi Sun, Jinlan Jiao, Anya Buerliesi, Li Li, Yun Zhu, Weijie Zhang
To address the issue of PD-1 inhibitor resistance driven by the immunosuppressive tumor microenvironment in triple-negative breast cancer (TNBC), we constructed activated platelet membrane-derived vesicles for targeted delivery of hemopexin (HPX) small interfering RNA (siRNA) (APP@siHPX), which effectively reduced the extracellular transport of heme and inhibited heme-mediated thrombospondin-1 (TSP-1) release, leading to decreased tumor-associated macrophage (TAM) recruitment and reprogramming of TAMs from the M2 phenotype to the M1 phenotype. Consequently, combining APP@siHPX with PD-1 inhibitors synergistically alleviates T-cell immunosuppression and increases CD8+ T-cell activity, resulting in significant tumor growth inhibition. In summary, our results demonstrate that targeting the HPX-heme-TSP-1 axis via APP@siHPX represents a promising strategy for enhancing the efficacy of immune checkpoint inhibitors in TNBC.
{"title":"Targeting inhibiting recruitment of macrophages with siHPX loading activated platelet vesicle for synergizing with PD-1 inhibitors in triple-negative breast cancer","authors":"Yue Long, Jie Ling, Wenqian Wei, Yi Lv, Xiaoling Guo, Yi Sun, Jinlan Jiao, Anya Buerliesi, Li Li, Yun Zhu, Weijie Zhang","doi":"10.26599/nr.2025.94907875","DOIUrl":"https://doi.org/10.26599/nr.2025.94907875","url":null,"abstract":"To address the issue of PD-1 inhibitor resistance driven by the immunosuppressive tumor microenvironment in triple-negative breast cancer (TNBC), we constructed activated platelet membrane-derived vesicles for targeted delivery of hemopexin (HPX) small interfering RNA (siRNA) (APP@siHPX), which effectively reduced the extracellular transport of heme and inhibited heme-mediated thrombospondin-1 (TSP-1) release, leading to decreased tumor-associated macrophage (TAM) recruitment and reprogramming of TAMs from the M2 phenotype to the M1 phenotype. Consequently, combining APP@siHPX with PD-1 inhibitors synergistically alleviates T-cell immunosuppression and increases CD8<sup>+</sup> T-cell activity, resulting in significant tumor growth inhibition. In summary, our results demonstrate that targeting the HPX-heme-TSP-1 axis via APP@siHPX represents a promising strategy for enhancing the efficacy of immune checkpoint inhibitors in TNBC.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"19 1","pages":"94907875-94907875"},"PeriodicalIF":0.0,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sciopen.com/article_pdf/1952250469696446465.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The advancement of efficient and environmentally sustainable heterogeneous catalysts that facilitate the transformation of carbon dioxide (CO2) into chemicals has gained considerable attention. In this study, we synthesized a carbon nitride (C3N4) functionalized with copper phthalocyanine (CuPc) and ionic liquid (IL) (C3N4-CuPc-IL) and employed it as an efficient catalyst enabling the cycloaddition of CO2 with epoxides. The presence of urea/urethane groups, Cu2+ ions, and I- ions that can effectively activate and open the epoxide ring was confirmed by FTIR, XPS, UV-vis, TGA, XRD and SEM. Meanwhile, the multiple nitrogen-containing structures (copper phthalocyanine, C3N4, and quaternary ammonium cationic structures) facilitated the adsorption and activation of CO2. Consequently, C3N4-CuPc-IL demonstrated high catalytic efficiency for the cycloaddition between CO2 and epoxides. Specifically, with 5.0 wt% loading of C3N4-CuPc-IL catalyst under 2.0 MPa and 120 °C for 12 h, the yield of cyclic carbonate reached 98%. Additionally, the prepared catalyst demonstrated excellent structural stability and recyclability, alongside high catalytic activity toward various epoxides. Density functional theory (DFT) calculations indicated that the ring-opening reaction represents the rate-determining step in the C3N4-CuPc-IL catalyzed cycloaddition reaction, with an energy barrier of only 24.2 kcal•mol-1. The impressive catalytic performance of C3N4-CuPc-IL confirmed the synergistic catalytic effect of hydrogen bond donor groups, Lewis acidic sites, and ionic active sites in the CO2 cycloaddition reaction, providing theoretical guidance for the design of CO2 conversion catalysts.
促进二氧化碳（CO2）转化为化学品的高效和环境可持续的多相催化剂的进展已经引起了相当大的关注。在本研究中，我们合成了一种由酞菁铜（CuPc）和离子液体（IL） （C3N4- cup -IL）功能化的氮化碳（C3N4），并将其作为催化剂用于二氧化碳与环氧化物的环加成反应。通过FTIR、XPS、UV-vis、TGA、XRD和SEM等手段证实了尿素/聚氨酯基团、Cu2+离子和I-离子能有效激活和打开环氧环。同时，多种含氮结构（酞菁铜、C3N4和季铵阳离子结构）有利于CO2的吸附和活化。结果表明，c3n4 - cup - il对CO2与环氧化物之间的环加成反应具有较高的催化效率。其中，c3n4 - cup - il催化剂负载5.0 wt%，在2.0 MPa、120℃条件下反应12 h，环碳酸酯收率可达98%。此外，所制备的催化剂具有良好的结构稳定性和可回收性，对各种环氧化物具有较高的催化活性。密度泛函理论（DFT）计算表明，开环反应是c3n4 - cupco - il催化环加成反应的速率决定步骤，其能垒仅为24.2 kcal•mol-1。c3n4 - cupco - il令人印象深刻的催化性能证实了氢键给体基团、Lewis酸位和离子活性位在CO2环加成反应中的协同催化作用，为CO2转化催化剂的设计提供了理论指导。
{"title":"Copper phthalocyanine and ionic liquid functionalized carbon nitride for catalytic cycloaddition of carbon dioxide","authors":"Qingqing Hou, Zhen-Hua Dang, Yue Yu, Xiufu Hua, Mingsong Wu, Lingling Wang, Renbo Wei","doi":"10.26599/nr.2025.94907846","DOIUrl":"https://doi.org/10.26599/nr.2025.94907846","url":null,"abstract":"The advancement of efficient and environmentally sustainable heterogeneous catalysts that facilitate the transformation of carbon dioxide (CO<sub>2</sub>) into chemicals has gained considerable attention. In this study, we synthesized a carbon nitride (C<sub>3</sub>N<sub>4</sub>) functionalized with copper phthalocyanine (CuPc) and ionic liquid (IL) (C<sub>3</sub>N<sub>4</sub>-CuPc-IL) and employed it as an efficient catalyst enabling the cycloaddition of CO<sub>2</sub> with epoxides. The presence of urea/urethane groups, Cu<sup>2+</sup> ions, and I<sup>-</sup> ions that can effectively activate and open the epoxide ring was confirmed by FTIR, XPS, UV-vis, TGA, XRD and SEM. Meanwhile, the multiple nitrogen-containing structures (copper phthalocyanine, C<sub>3</sub>N<sub>4</sub>, and quaternary ammonium cationic structures) facilitated the adsorption and activation of CO<sub>2</sub>. Consequently, C<sub>3</sub>N<sub>4</sub>-CuPc-IL demonstrated high catalytic efficiency for the cycloaddition between CO<sub>2</sub> and epoxides. Specifically, with 5.0 wt% loading of C<sub>3</sub>N<sub>4</sub>-CuPc-IL catalyst under 2.0 MPa and 120 °C for 12 h, the yield of cyclic carbonate reached 98%. Additionally, the prepared catalyst demonstrated excellent structural stability and recyclability, alongside high catalytic activity toward various epoxides. Density functional theory (DFT) calculations indicated that the ring-opening reaction represents the rate-determining step in the C<sub>3</sub>N<sub>4</sub>-CuPc-IL catalyzed cycloaddition reaction, with an energy barrier of only 24.2 kcal•mol<sup>-1</sup>. The impressive catalytic performance of C<sub>3</sub>N<sub>4</sub>-CuPc-IL confirmed the synergistic catalytic effect of hydrogen bond donor groups, Lewis acidic sites, and ionic active sites in the CO<sub>2</sub> cycloaddition reaction, providing theoretical guidance for the design of CO<sub>2</sub> conversion catalysts.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"18 11","pages":"94907846-94907846"},"PeriodicalIF":0.0,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sciopen.com/article_pdf/1949659272863850498.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-25DOI: 10.26599/nr.2025.94907827
Haiheng Xu, Shuqin Xiong, Dewen Zheng, Lan An, Yiyun Chen, Lei Wang, Xuehui Rui, Jinhui Wu
Despite the promise of nanomedicines leveraging the enhanced permeability and retention (EPR) effect for tumor targeting, their clinical translation remains hindered due to physiological barriers, rapid clearance, and poor intratumoral diffusion. In situ self-assembly of nanomedicines within tumors offers a promising strategy to enhance tumor accumulation. However, significant challenges persist. Herein, our findings reveal that tumor-infiltrating erythrocytes demonstrate the capacity to endogenously synthesize self-assembled nanomedicine with clinically approved small-molecule drug. Attenuated Salmonella Typhimurium VNP20009 (VNP) can induce tumor-specific erythrocyte infiltration. Erythrocytes infiltrating the tumor site are phagocytosed by tumor cells and degraded into ferrous ions through the action of heme oxygenase. In the presence of zoledronic acid, ferrous irons interact with the zoledronic acid, resulting in the intracellular self-assembly of nanoparticles within tumor cells. These nanoparticles exhibit peroxidase-mimetic activity, and continuously catalyze the generation of reactive oxygen species (ROS) within the tumor, ultimately inducing tumor cell apoptosis. Therefore, this bioengineered therapeutic strategy that harnesses erythrocyte phagocytosis to drive tumor-specific intracellular self-assembly of peroxidase-mimetic nanoparticles may open up new nanotechnology for drug delivery and improve antitumor therapy.
{"title":"Tumor intracellular self-assembled nanoparticles induced by bacteria elicited erythrocyte infiltration realize antitumor efficacy of zoledronate","authors":"Haiheng Xu, Shuqin Xiong, Dewen Zheng, Lan An, Yiyun Chen, Lei Wang, Xuehui Rui, Jinhui Wu","doi":"10.26599/nr.2025.94907827","DOIUrl":"https://doi.org/10.26599/nr.2025.94907827","url":null,"abstract":"Despite the promise of nanomedicines leveraging the enhanced permeability and retention (EPR) effect for tumor targeting, their clinical translation remains hindered due to physiological barriers, rapid clearance, and poor intratumoral diffusion. <i>In situ</i> self-assembly of nanomedicines within tumors offers a promising strategy to enhance tumor accumulation. However, significant challenges persist. Herein, our findings reveal that tumor-infiltrating erythrocytes demonstrate the capacity to endogenously synthesize self-assembled nanomedicine with clinically approved small-molecule drug. Attenuated <i>Salmonella Typhimurium</i> VNP20009 (VNP) can induce tumor-specific erythrocyte infiltration. Erythrocytes infiltrating the tumor site are phagocytosed by tumor cells and degraded into ferrous ions through the action of heme oxygenase. In the presence of zoledronic acid, ferrous irons interact with the zoledronic acid, resulting in the intracellular self-assembly of nanoparticles within tumor cells. These nanoparticles exhibit peroxidase-mimetic activity, and continuously catalyze the generation of reactive oxygen species (ROS) within the tumor, ultimately inducing tumor cell apoptosis. Therefore, this bioengineered therapeutic strategy that harnesses erythrocyte phagocytosis to drive tumor-specific intracellular self-assembly of peroxidase-mimetic nanoparticles may open up new nanotechnology for drug delivery and improve antitumor therapy.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"18 9","pages":"94907827-94907827"},"PeriodicalIF":0.0,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, we propose an innovative flexible cathode design for zinc-ion batteries (ZIBs) through the strategic integration of sodium vanadate (NaV3O8·1.5H2O) with two-dimensional MXene nanosheets (Ti3C2 or Mo2C). The composite architecture leverages MXene’s dual advantages of exceptional electrical conductivity and surface hydrophilicity to significantly enhance the electrochemical performance of the vanadate host. The NaV3O8·1.5H2O was synthesized through a reaction between V2O5 and NaCl aqueous solution, followed by hybridization with MXene in NaCl solution. When configured into full cells with zinc foil anode and 3 M Zn(CF3SO3)2 electrolyte, the optimized composite with 11 wt.% Ti3C2 MXene demonstrates remarkable electrochemical enhancement, delivering a specific capacity of 339.6 mAh/g at 1 A/g, a 30.86% improvement over pristine NaV3O8·1.5H2O (259.5 mAh/g). The MXene-modified cathode exhibits extraordinary cycling stability with near 100% capacity retention after 3800 cycles at 3 A/g, outperforming the pure vanadate counterpart that degrades to 103.6 mAh/g after only 2000 cycles. A capacity improvement, the incorporation of MXene also increases the structural stability of the cathode during flexible test cycles. It maintains a capacity of 227.9 mAh/g at 1 A/g under extreme 90° bending/twisting deformations. This synergistic combination of high energy density (381.5 mAh/g at 0.1 A/g), ultralong cycle life, and mechanical endurance positions the MXene-vanadate composite as a promising candidate for next-generation flexible energy storage systems.
在此，我们提出了一种创新的锌离子电池（ZIBs）柔性阴极设计，通过将钒酸钠（NaV3O8·1.5H2O）与二维MXene纳米片（Ti3C2或Mo2C）战略集成。复合结构利用了MXene优异的导电性和表面亲水性的双重优势，显著提高了钒酸盐主体的电化学性能。通过V2O5与NaCl水溶液反应合成了NaV3O8·1.5H2O，并在NaCl溶液中与MXene杂化。当以锌箔阳极和3 M Zn(CF3SO3)2电解质配置为全电池时，优化后的复合材料Ti3C2 MXene含量为11 wt.%，表现出显著的电化学增强，在1 a /g时的比容量为339.6 mAh/g，比原始的NaV3O8·1.5H2O （259.5 mAh/g）提高了30.86%。mxene修饰的阴极具有非凡的循环稳定性，在3 A/g下循环3800次后，其容量保持率接近100%，优于纯钒酸盐阴极，仅在2000次循环后就退化到103.6 mAh/g。容量的提高，MXene的加入也增加了阴极在柔性测试循环中的结构稳定性。在极端的90°弯曲/扭转变形下，它在1 a /g时保持227.9 mAh/g的容量。这种高能量密度（0.1 A/g时381.5 mAh/g）、超长循环寿命和机械耐久性的协同组合，使MXene-vanadate复合材料成为下一代柔性储能系统的有希望的候选者。
{"title":"Boosting the performance of sodium vanadate as cathode of flexible zinc-ion batteries by incorporating MXenes","authors":"Guanglei Zhang, Jiacheng Fan, Jilin Gou, Xiaole Zhao, Jingdi Shang, Libo Wang, Yukai Chang, Aiguo Zhou","doi":"10.26599/nr.2025.94907786","DOIUrl":"https://doi.org/10.26599/nr.2025.94907786","url":null,"abstract":"Herein, we propose an innovative flexible cathode design for zinc-ion batteries (ZIBs) through the strategic integration of sodium vanadate (NaV<sub>3</sub>O<sub>8</sub>·1.5H<sub>2</sub>O) with two-dimensional MXene nanosheets (Ti<sub>3</sub>C<sub>2</sub> or Mo<sub>2</sub>C). The composite architecture leverages MXene’s dual advantages of exceptional electrical conductivity and surface hydrophilicity to significantly enhance the electrochemical performance of the vanadate host. The NaV<sub>3</sub>O<sub>8</sub>·1.5H<sub>2</sub>O was synthesized through a reaction between V<sub>2</sub>O<sub>5</sub> and NaCl aqueous solution, followed by hybridization with MXene in NaCl solution. When configured into full cells with zinc foil anode and 3 M Zn(CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub> electrolyte, the optimized composite with 11 wt.% Ti<sub>3</sub>C<sub>2</sub> MXene demonstrates remarkable electrochemical enhancement, delivering a specific capacity of 339.6 mAh/g at 1 A/g, a 30.86% improvement over pristine NaV<sub>3</sub>O<sub>8</sub>·1.5H<sub>2</sub>O (259.5 mAh/g). The MXene-modified cathode exhibits extraordinary cycling stability with near 100% capacity retention after 3800 cycles at 3 A/g, outperforming the pure vanadate counterpart that degrades to 103.6 mAh/g after only 2000 cycles. A capacity improvement, the incorporation of MXene also increases the structural stability of the cathode during flexible test cycles. It maintains a capacity of 227.9 mAh/g at 1 A/g under extreme 90° bending/twisting deformations. This synergistic combination of high energy density (381.5 mAh/g at 0.1 A/g), ultralong cycle life, and mechanical endurance positions the MXene-vanadate composite as a promising candidate for next-generation flexible energy storage systems.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"18 10","pages":"94907786-94907786"},"PeriodicalIF":0.0,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciopen.com/local/article_pdf/10.26599/NR.2025.94907786.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-11DOI: 10.26599/nr.2025.94907768
Xinyu Liu, Wanlin Zhou, Yuhao Zhang, Qizheng An, Jingjing Jiang, Youcai Che, Xupeng Qin, Hong Sun, Qinghua Liu, Shiqiang Wei
Rational modulation of Fe-N4 coordination symmetry through heteroatom doping with distinct electronegativities has emerged as a promising strategy to optimize the performance of the oxygen reduction reaction (ORR). Here, we systematically investigate the less electronegative sulfur- and phosphorus-doped Fe single-atom catalysts and demonstrate that the S-doped catalyst (Fe-SNC) achieves superior ORR activity (E1/2 = 0.904 V vs. RHE), surpassing both the P-doped Fe-PNC (0.872 V) and undoped Fe-NC control samples while maintaining exceptional durability. Synchrotron radiation X-ray absorption spectroscopy verified the precise engineering of the asymmetric Fe-S1N3 and Fe-P1N3 configurations within the ZIF-8-derived carbon matrices, confirming successful manipulation of the first coordination sphere. In situ synchrotron radiation infrared spectroscopy further elucidates accelerated *OOH dissociation kinetics in Fe-SNC, which benefits from the optimization of the electronic structure of Fe 3d by S doping. These findings conclusively establish geometric symmetry breaking via electronegativity-driven electronic modulation as an effective strategy for advancing metal-N4 catalyst design.
通过不同电负性的杂原子掺杂合理调制Fe-N4配位对称性是优化氧还原反应（ORR）性能的一种有前途的策略。在此，我们系统地研究了电负性较低的硫和磷掺杂铁单原子催化剂，并证明了s掺杂催化剂（Fe- snc）具有优越的ORR活性（E1/2 = 0.904 V vs. RHE），超过了p掺杂Fe- pnc （0.872 V）和未掺杂Fe- nc对照样品，同时保持了优异的耐久性。同步辐射x射线吸收光谱验证了不对称Fe-S1N3和Fe-P1N3构型在zif -8衍生碳基体中的精确工程，证实了第一配位球的成功操纵。原位同步辐射红外光谱进一步阐明了Fe- snc中*OOH加速解离动力学，这得益于S掺杂对Fe 3d电子结构的优化。这些发现最终确定了通过电负性驱动的电子调制来实现几何对称性破缺是推进金属- n4催化剂设计的有效策略。
{"title":"Engineering the first coordination sphere of FeN <sub>4</sub> sites with less electronegative heteroatoms for oxygen reduction catalysis","authors":"Xinyu Liu, Wanlin Zhou, Yuhao Zhang, Qizheng An, Jingjing Jiang, Youcai Che, Xupeng Qin, Hong Sun, Qinghua Liu, Shiqiang Wei","doi":"10.26599/nr.2025.94907768","DOIUrl":"https://doi.org/10.26599/nr.2025.94907768","url":null,"abstract":"Rational modulation of Fe-N<sub>4</sub> coordination symmetry through heteroatom doping with distinct electronegativities has emerged as a promising strategy to optimize the performance of the oxygen reduction reaction (ORR). Here, we systematically investigate the less electronegative sulfur- and phosphorus-doped Fe single-atom catalysts and demonstrate that the S-doped catalyst (Fe-SNC) achieves superior ORR activity (E<sub>1/2</sub> = 0.904 V vs. RHE), surpassing both the P-doped Fe-PNC (0.872 V) and undoped Fe-NC control samples while maintaining exceptional durability. Synchrotron radiation X-ray absorption spectroscopy verified the precise engineering of the asymmetric Fe-S<sub>1</sub>N<sub>3</sub> and Fe-P<sub>1</sub>N<sub>3</sub> configurations within the ZIF-8-derived carbon matrices, confirming successful manipulation of the first coordination sphere. In situ synchrotron radiation infrared spectroscopy further elucidates accelerated *OOH dissociation kinetics in Fe-SNC, which benefits from the optimization of the electronic structure of Fe 3<em>d</em> by S doping. These findings conclusively establish geometric symmetry breaking via electronegativity-driven electronic modulation as an effective strategy for advancing metal-N<sub>4</sub> catalyst design.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"18 12","pages":"94907768-94907768"},"PeriodicalIF":0.0,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sciopen.com/article_pdf/1943188345942798337.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-10DOI: 10.26599/nr.2025.94907764
Ruichen Lu, Shanshan Wang, Lan Jiang, Xianze Zhang, Zikang Su, Chen Zhang, Qimiao Zhu, Shilong Yuan, Xueqiang Zhang
The electrochemical conversion of CO2 into value-added chemicals presents an environmentally sustainable alternative to conventional fossil-derived processes, yet achieving high selectivity remains challenging due to competing reaction pathways. Here, we demonstrate precise tuning of CO2 electroreduction pathways through femtosecond laser-driven surface doping of Cu with targeted metals, achieving Faradaic efficiencies of 58.9% for CO, 67.9% for formate, and 37.8% for ethylene. This spatially shaping laser technique enables nanoscale deposition of any metal (including Sb, Sn, Re, La, In, Co, Ni, Ag, Pt) onto Cu foil, forming compositionally graded Cu-based bimetallic surfaces with controlled atomic ratios. Systematic electronic structure analysis reveals that secondary metals induce d-band center shifts spanning -0.21 to +0.78 eV, governing intermediate adsorption energetics-upward shifts strengthen *CO binding via enhanced back-donation, while downward generally shifts weaken adsorbate interactions. Through precise control of Cu/Sn and Cu/Sb atomic ratios, we manipulate electronic structures of CuSn and CuSb catalysts and consequently demonstrate continuous tuning of formate (19.0–67.9%) and CO (18.8–58.9%) selectivity. In-situ Raman spectroscopy and valence band XPS elucidate dual modulation mechanisms, Sn enhances CO desorption by weakening *CO adsorption, whereas La promotes ethylene formation through optimized CO absorption and dimerization. The tunability of the reaction pathways align with metal-dependent stabilization of critical intermediates (CO, *OCHO). This work introduces a nanoscale-depth and trace-level multi-elemental loading strategy with tunable ratios on copper electrodes, enabling precise electronic structure manipulation of Cu-based electrocatalysts to mechanistically elucidate the correlation between surface electronic states and product selectivity, offering a roadmap to design and modulate Cu-based catalysts for selective CO2-to-chemical conversion and beyond via low-cost laser processing techniques.
电化学将二氧化碳转化为增值化学品是传统化石衍生工艺的一种环境可持续替代方法，但由于反应途径的竞争，实现高选择性仍然具有挑战性。在这里，我们展示了通过飞秒激光驱动的铜表面掺杂靶金属来精确调整CO2电还原途径，实现了CO的法拉第效率为58.9%，甲酸为67.9%，乙烯为37.8%。这种空间成形激光技术可以将任何金属（包括Sb， Sn, Re, La, In, Co, Ni, Ag, Pt）纳米级沉积到铜箔上，形成具有可控原子比的成分梯度的Cu基双金属表面。系统的电子结构分析表明，次生金属诱导的d带中心位移跨越-0.21 ~ +0.78 eV，控制了中间吸附能量，向上的位移增强了*CO的结合，而向下的一般位移减弱了吸附物的相互作用。通过精确控制Cu/Sn和Cu/Sb原子比，我们操纵了CuSn和CuSb催化剂的电子结构，从而实现了甲酸（19.0-67.9%）和CO（18.8-58.9%）选择性的连续调整。原位拉曼光谱和价带XPS分析表明，锡通过减弱*CO吸附来促进CO的脱附，而镧通过优化CO吸附和二聚化来促进乙烯的生成。反应途径的可调性与关键中间体（CO, *OCHO）的金属依赖稳定性一致。这项工作介绍了一种纳米级深度和痕量级多元素负载策略，铜电极上的可调比例，使cu基电催化剂的精确电子结构操纵能够机械地阐明表面电子状态与产物选择性之间的关系，为设计和调节cu基催化剂提供了路线图，通过低成本的激光加工技术进行选择性的二氧化碳到化学转化。
{"title":"Tailoring electrocatalytic CO <sub>2</sub> reduction pathways with femtosecond laser facilitated elemental doping of Cu foil","authors":"Ruichen Lu, Shanshan Wang, Lan Jiang, Xianze Zhang, Zikang Su, Chen Zhang, Qimiao Zhu, Shilong Yuan, Xueqiang Zhang","doi":"10.26599/nr.2025.94907764","DOIUrl":"https://doi.org/10.26599/nr.2025.94907764","url":null,"abstract":"The electrochemical conversion of CO<sub>2</sub> into value-added chemicals presents an environmentally sustainable alternative to conventional fossil-derived processes, yet achieving high selectivity remains challenging due to competing reaction pathways. Here, we demonstrate precise tuning of CO<sub>2</sub> electroreduction pathways through femtosecond laser-driven surface doping of Cu with targeted metals, achieving Faradaic efficiencies of 58.9% for CO, 67.9% for formate, and 37.8% for ethylene. This spatially shaping laser technique enables nanoscale deposition of any metal (including Sb, Sn, Re, La, In, Co, Ni, Ag, Pt) onto Cu foil, forming compositionally graded Cu-based bimetallic surfaces with controlled atomic ratios. Systematic electronic structure analysis reveals that secondary metals induce d-band center shifts spanning -0.21 to +0.78 eV, governing intermediate adsorption energetics-upward shifts strengthen *CO binding via enhanced back-donation, while downward generally shifts weaken adsorbate interactions. Through precise control of Cu/Sn and Cu/Sb atomic ratios, we manipulate electronic structures of CuSn and CuSb catalysts and consequently demonstrate continuous tuning of formate (19.0–67.9%) and CO (18.8–58.9%) selectivity. I<em>n</em><em>-situ</em> Raman spectroscopy and valence band XPS elucidate dual modulation mechanisms, Sn enhances CO desorption by weakening *CO adsorption, whereas La promotes ethylene formation through optimized CO absorption and dimerization. The tunability of the reaction pathways align with metal-dependent stabilization of critical intermediates (CO, *OCHO). This work introduces a nanoscale-depth and trace-level multi-elemental loading strategy with tunable ratios on copper electrodes, enabling precise electronic structure manipulation of Cu-based electrocatalysts to mechanistically elucidate the correlation between surface electronic states and product selectivity, offering a roadmap to design and modulate Cu-based catalysts for selective CO<sub>2</sub>-to-chemical conversion and beyond via low-cost laser processing techniques.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"18 11","pages":"94907764-94907764"},"PeriodicalIF":0.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sciopen.com/article_pdf/1943136098894499842.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The precise manipulation of chiral crystallization for the fabrication of homochiral surfaces has emerged as a pivotal focal point within the realm of surface chemistry. In this investigation, we employed a temperature-regulated strategy, utilizing the conformationally chiral molecule 1, 1, 2, 2-Tetrakis(4-bromophenyl)ethene (TPEB) as a precursor to control the chiral recognition and separation process on Ag(111) surface mediated through Br···H and Br···Br interactions. At a temperature of 77 K, when TPEB was deposited onto the Ag(111) surface, it gives rise to two mirror-image racemic structures. As the temperature increases, TPEB molecules undergo a distinct transition from existing in racemic mixtures to enantiomeric excess mixtures. This transition ultimately culminates in a chiral separation process, resulting in the formation of a single-handed self-assembled structure and the acquisition of a homochiral Kagomé lattice. This work meticulously monitored the chiral crystallization process of the conformationally chiral molecules on Ag(111) surface, capturing structures with diverse enantiomeric compositions. Moreover, through a combination of molecular simulations and density functional theory (DFT) calculations, we elucidated that an increase in temperature enhances the recognition between chiral molecules of the same handedness. This enhanced recognition, in turn, promotes the chiral separation process and steers the transition of the supramolecular assemblies from racemic mixtures towards single-handed structures. This study not only achieved the separation of heterochiral molecular conformations but also paved an effective avenue for the fabrication of homochiral nanostructures.
{"title":"Temperature-induced unbalanced chiral crystallization from racemic to nonracemic to homochiral lattice on Ag(111)","authors":"Minjie Xu, Xiushan Zhang, Qi Chen, Shu-Ying Li, Guangshan Zhu","doi":"10.26599/nr.2025.94907758","DOIUrl":"https://doi.org/10.26599/nr.2025.94907758","url":null,"abstract":"The precise manipulation of chiral crystallization for the fabrication of homochiral surfaces has emerged as a pivotal focal point within the realm of surface chemistry. In this investigation, we employed a temperature-regulated strategy, utilizing the conformationally chiral molecule 1, 1, 2, 2-Tetrakis(4-bromophenyl)ethene (TPEB) as a precursor to control the chiral recognition and separation process on Ag(111) surface mediated through Br···H and Br···Br interactions. At a temperature of 77 K, when TPEB was deposited onto the Ag(111) surface, it gives rise to two mirror-image racemic structures. As the temperature increases, TPEB molecules undergo a distinct transition from existing in racemic mixtures to enantiomeric excess mixtures. This transition ultimately culminates in a chiral separation process, resulting in the formation of a single-handed self-assembled structure and the acquisition of a homochiral Kagomé lattice. This work meticulously monitored the chiral crystallization process of the conformationally chiral molecules on Ag(111) surface, capturing structures with diverse enantiomeric compositions. Moreover, through a combination of molecular simulations and density functional theory (DFT) calculations, we elucidated that an increase in temperature enhances the recognition between chiral molecules of the same handedness. This enhanced recognition, in turn, promotes the chiral separation process and steers the transition of the supramolecular assemblies from racemic mixtures towards single-handed structures. This study not only achieved the separation of heterochiral molecular conformations but also paved an effective avenue for the fabrication of homochiral nanostructures.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"18 12","pages":"94907758-94907758"},"PeriodicalIF":0.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sciopen.com/article_pdf/1942771950197166082.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331547","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-02DOI: 10.26599/nr.2025.94907745
Han Li-hua, Zhiya Dang, Yiran Xi, Liangliang Zhu, Su Chen
Direct conversion of CO2 to chemical fuels by photocatalysis has emerged as a promising strategy to alleviate global warming and renewable energy shortage issues. Halide perovskites with unique photoelectronic attributes show great potential for CO2 photoreduction. However, their low photogenerated electron-hole efficiency and intrinsic structural instability in aqueous solution are still a significant challenge. In this work, we propose a universal facile strategy of robust carbon dots (CDs) mediated inverse opal perovskite (IOP) free-standing film, which is demonstrated as a uniform porous photocatalytic platform where efficient CO2 photoreduction. Due to the grain boundary passivation effect of CDs, the mechanical strength and water resistance of CDs/IOP films are greatly improved. By the synergetic effects of IO structure and CDs cocatalyst, highly selective CO evolution rate of 60.25 μmol·g-1·h-1 from photocatalytic CO2 reduction is achieved on typical CDs/CsPbBr3 IOP film, which is 15.6 times higher than that of opal CsPbBr3 since the enhanced lifetime of photogenerated electrons-holes and light/mass transfers. This work provides a new opportunity for robust and highly stable perovskite photocatalyst preparation to address the environmental and energy issues via an efficient photocatalysis process.
{"title":"Carbon-dots-mediated flexible inverse opal perovskite film featuring structural robustness and highly selective photocatalytic CO <sub>2</sub> reduction","authors":"Han Li-hua, Zhiya Dang, Yiran Xi, Liangliang Zhu, Su Chen","doi":"10.26599/nr.2025.94907745","DOIUrl":"https://doi.org/10.26599/nr.2025.94907745","url":null,"abstract":"Direct conversion of CO<sub>2</sub> to chemical fuels by photocatalysis has emerged as a promising strategy to alleviate global warming and renewable energy shortage issues. Halide perovskites with unique photoelectronic attributes show great potential for CO<sub>2</sub> photoreduction. However, their low photogenerated electron-hole efficiency and intrinsic structural instability in aqueous solution are still a significant challenge. In this work, we propose a universal facile strategy of robust carbon dots (CDs) mediated inverse opal perovskite (IOP) free-standing film, which is demonstrated as a uniform porous photocatalytic platform where efficient CO<sub>2</sub> photoreduction. Due to the grain boundary passivation effect of CDs, the mechanical strength and water resistance of CDs/IOP films are greatly improved. By the synergetic effects of IO structure and CDs cocatalyst, highly selective CO evolution rate of 60.25 μmol·g-1·h-1 from photocatalytic CO<sub>2</sub> reduction is achieved on typical CDs/CsPbBr<sub>3</sub> IOP film, which is 15.6 times higher than that of opal CsPbBr<sub>3</sub> since the enhanced lifetime of photogenerated electrons-holes and light/mass transfers. This work provides a new opportunity for robust and highly stable perovskite photocatalyst preparation to address the environmental and energy issues via an efficient photocatalysis process.","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"18 11","pages":"94907745-94907745"},"PeriodicalIF":0.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sciopen.com/article_pdf/1940216184076554241.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-01Epub Date: 2025-05-22DOI: 10.26599/nr.2025.94907534
Mengwen Li, Wenpan Li, Zhi Li, Jianqin Lu
Peptide-based vaccines only contain peptide epitopes and exclude unnecessary biological materials, which greatly reduces the risk of causing an undesired immune response and further improves the safety profile, garnering considerable interest in vaccine development. However, the immunogenicity induced by these peptides alone is not potent enough to elicit an effective immune response. Recently, combining the adjuvants with peptide antigens has shown promising effects to realize a satisfying immune response. In this review, we discuss the development of immunoadjuvants to enhance the safety and efficacy of peptide-based vaccines. The emphasis is placed on the application and clinical translation of nanotechnology-based adjuvants, highlighting the associated challenges and exploring future directions.
{"title":"Advances in nanotechnology-enabled adjuvants for peptide-based cancer vaccines.","authors":"Mengwen Li, Wenpan Li, Zhi Li, Jianqin Lu","doi":"10.26599/nr.2025.94907534","DOIUrl":"https://doi.org/10.26599/nr.2025.94907534","url":null,"abstract":"<p><p>Peptide-based vaccines only contain peptide epitopes and exclude unnecessary biological materials, which greatly reduces the risk of causing an undesired immune response and further improves the safety profile, garnering considerable interest in vaccine development. However, the immunogenicity induced by these peptides alone is not potent enough to elicit an effective immune response. Recently, combining the adjuvants with peptide antigens has shown promising effects to realize a satisfying immune response. In this review, we discuss the development of immunoadjuvants to enhance the safety and efficacy of peptide-based vaccines. The emphasis is placed on the application and clinical translation of nanotechnology-based adjuvants, highlighting the associated challenges and exploring future directions.</p>","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"18 7","pages":""},"PeriodicalIF":9.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12362341/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144938382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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