Co(Ⅱ) coordination polymers: Structural characterization and fluorescence sensing of Al3+ in aqueous
【无机化学学报】doi: 10.11862/CJIC.20250114
Complexes [Co(hfacac)2(L1)]n (1) and [Co(hfacac)(L2)]n (2) (Hhfacac=hexafluoroacetylacetonate) were synthesized by coordinating Co(hfacac)2 with ligands 3, 6-di(pyridin-4-yl)-9H-carbazole (L1) and 9-methyl-3, 6-di(pyridin-4-yl)-9H-carbazole (L2), respectively. The complexes were characterized by infrared spectrometry, UV-Vis spectrometry, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that complex 2 crystallizes in a triclinic crystal system with the space group P1, and the unit cell volume is 1.928 7(2) nm3. The Co(Ⅱ) centers exhibit distorted octahedral coordination. One-dimensional chain structures of 2 are stabilized by hydrogen bonding and π-π stacking interactions. Fluorescence studies showed that complex 1 could be highly selective in Al3+ detection with a limit of detection of 51.3 nmol·L-1 and had a significant turn-on response to Al3+, which is attributed to the chelation-enhanced fluorescence (CHEF) mechanism. Furthermore, fluorescent test strips were developed for rapid in situ detection of Al3+.
【物理化学学报】doi: 10.3866/PKU.WHXB202305047
利用取之不尽的太阳能资源进行光催化水裂解制氢是缓解全球能源危机、实现碳中和战略的一项有前景的技术。石墨相氮化碳(g-C3N4)因成本低且稳定性高在光催化产氢领域备受关注。然而,纯g-C3N4存在表面积小、电子转移慢、光生载流子复合快等缺陷,产氢性能通常不佳。本研究通过直接热解硫酸铵和三聚氰胺混合物,成功实现硫物种对g-C3N4氮位点的原位取代,开发出一种高效的硫掺杂g-C3N4 (S-g-CN)光催化剂。系列结构和光谱表征证实硫的成功掺杂。密度泛函理论的第一性原理计算表明S活性位对氢的吸附吉布斯自由能近乎为零(~0.26 eV),揭示S掺杂在优化H活性中间体吸附和解吸过程中起着重要作用。透射电子显微镜和原子力显微镜测试结果表明,S-g-CN具有超薄的纳米片状结构,其片层厚度约为2.5 nm。随后的氮气吸脱附等温线和光电化学性质测试结果表明,S掺杂不仅可显著增大g-C3N4比表面积,而且还能有效提高其光生电子-空穴对的转移、分离和氧化还原能力。得益于材料良好的结构特性,S-g-CN的光催化产氢速率高达4923 μmol∙g−1∙h−1,是原始g-C3N4的28倍,超越诸多最近报道的其它S掺杂g-C3N4光催化剂。而且,S-g-CN的表观量子效率高达3.64%。本研究除了开发一种高效的光催化剂,还将为高性能g-C3N4基催化剂的设计提供有益借鉴。
【物理化学学报】doi: 10.3866/PKU.WHXB202408005
化石燃料的燃烧导致CO2排放量显著增大,对环境构成严重威胁。光催化CO2还原是减少全球变暖的重要手段,本文探讨了石墨相氮化碳(g-C3N4)在此领域中的潜在应用。然而,光生载流子的复合较快、可见光吸收能力差以及缺乏活性位点等关键因素限制了g-C3N4的光催化CO2还原活性。为了解决这些问题,人们采用了多种改性策略,包括调整g-C3N4的形貌(如量子点、纳米棒、纳米管、纳米片、空心球等),掺杂不同类型原子,以及与其他半导体复合形成异质结。g-C3N4作为光催化剂已展现出光催化还原CO2的潜力,但仍需进一步研究和创新,本文重点讨论了S型异质结在提高g-C3N4光催化CO2还原性能方面的作用,以克服其当前催化剂开发及应用的局限性。
【无机化学学报】doi: 10.11862/CJIC.20250369
A composite catalyst (Ni-NiO@CN) with nickel-nickel oxide (Ni-NiO) loaded on two-dimensional g-C3N4 (CN) was successfully constructed by hydrothermal coupled pyrolysis. The Ni-NiO nanostructure served as the methanol oxidation reaction (MOR) active center, and the N-rich CN matrix promoted electron transfer and effectively protected the active components from shedding through physical isolation. Ni-NiO@CN-500, obtained by calcination at 500 ℃, exhibited the highest activity with the current density of 164 mA·cm-2 at 1.67 V (vs RHE) in the alkaline medium. Furthermore, the current density of Ni-NiO@CN-500 could be maintained at 154.9 mA·cm-2 (94.5% of its initial value) in the CO-saturated alkaline methanol electrolyte, significantly outperforming commercial Pt/C catalysts.
【无机化学学报】doi: 10.11862/CJIC.20240371
采用熔盐法制备出铝掺杂的钛酸锶(Al-SrTiO3),并通过水热法及气相氮化法在Al-SrTiO3表面紧密负载了Ni3N助催化剂。通过对Ni3N/Al-SrTiO3体系载流子转移特性表征以及密度泛函理论计算分析发现,Al-SrTiO3上的光生电子在费米能级差的作用下可快速转移到Ni3N上,有效促进了Al-SrTiO3上光生载流子的分离,从而提高其分解水析氢性能。光催化析氢测试结果表明,当Ni3N助催化剂负载量(Ni与Al-SrTiO3的质量比)为7%时,Al-SrTiO3的析氢速率相对负载前提升了82倍。
【无机化学学报】doi: 10.11862/CJIC.20250005
Two new complexes, [Zn2(L1)(HL1)(NO3)]·CH3OH (1) and [Zn3(L2)(L3)3Cl]·CH3OH (2), were successfully synthesized by'one-pot'method based on cinnoline-3-ylhydrazine ligand and zinc with 2-hydroxy-4-methoxybenz-aldehyde and 2-hydroxy-3-methoxybenzaldehyde ligands, respectively, where H2L1=5-methoxy-2-(phthalazin-1-yl-hydrazonomethyl)-phenol, H2L2=2-methoxy-6-(phthalazin-1-yl-hydrazonomethyl)-phenol, HL3=2-(1, 8-dihydro-[1,2,4]triazolo[3,4-α]phthalazin-3-yl)-6-methoxy-phenol. Complexes 1 and 2 were characterized by infrared spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction, etc. It is worth noting that the cinnolin-3-yl-hydrazine ligand and 2-hydroxy-3-methoxybenzaldehyde form two types of Schiff bases (H2L2 and HL3) when in situ reacting and coordinating with Zn(Ⅱ), and HL3 also has two coordination modes. In addition, the fluorescence performance showed that complex 1 can achieve selective and sensitive sensing of Al3+ in water with a detection limit of 6.37 μmol·L-1.
【物理化学学报】doi: 10.1016/j.actphy.2025.100054
等离子体活化非均相催化反应是在温和条件下实现CO2加氢反应的前沿策略。在本研究中,采用软模板法在Al2O3-x上构建了深孔通道结构。以Al2O3-x作为载体,通过浸渍法制备了Cu/Al2O3-x催化剂,并将其应用于等离子体催化CO2加氢制二甲醚(DME)反应。在等离子体催化CO2加氢反应中,Cu/Al2O3-0.75/HZSM-5展现出高性能和高放电效率。其等离子体催化CO2加氢的CO2转化率和DME产率分别达21.98%和9.83%,其中CO、CH3OH和DME的选择性分别为25.39%、29.89%和44.72%。Al2O3-x上的深孔道结构能够作为Cu的负载位点,同时介孔结构的限域效应增强了金属-载体之间的相互作用及Cu的金属分散度。更丰富且更强的Brønsted碱性和Lewis酸性位点促进了CO2的吸附、活化及加氢。值得注意地,锚定在深孔道结构中的Cu位点能够形成电场,从而引导等离子体活化CO2中间体进入难以接近的孔隙中进行加氢反应。深孔通道中等离子体活化CO2中间体的加氢对于提升等离子体催化CO2加氢制DME反应效率具有重要意义。
【物理化学学报】doi: 10.1016/j.actphy.2025.100046
面对由病原微生物感染引发疾病所带来的紧迫挑战,开发新型且高效的抗菌策略已成为当务之急。尽管光动力治疗在抗菌治疗领域已得到广泛应用,但在精确调控光敏剂结构以实现高效光动力性能方面仍存在一定的挑战。本文中,我们将铂单原子(SAs)锚定在二维(2D) Al-TCPP金属-有机框架(Pt/Al-TCPP)纳米片上,并将其用作光敏剂增强活性氧(ROS)的产生,实现高效的光动力抗菌治疗。通过将Pt SAs锚定到2D Al-TCPP纳米片上,我们不仅改善了Pt SAs的分散性和稳定性,还利用了MOF晶体多孔结构与Pt SAs之间的协同作用,优化了光子功能和光捕获能力。这种结构增强了Pt SAs与卟啉连接体之间的桥接单元,促进了光照下的高效电荷转移和分离,从而增强ROS的产生。同时,除了Pt SAs的固有光动力性能之外,它的存在还能增加氧气的吸附、加速电子转移、促进电荷分离,从而提高其光动力产生ROS的效率。因此,与Al-TCPP相比,Pt/Al-TCPP光敏剂在660 nm激光照射下显示出更高的ROS生成效率。体外和体内实验均表明,在激光照射下,较低剂量的Pt/Al-TCPP纳米片能够在较短时间内有效杀灭细菌并促进伤口愈合。本研究结果为抗菌策略的开发提供了新视角,并展示了Pt/Al-TCPP纳米片作为高效伤口愈合治疗剂的潜力。
【物理化学学报】doi: 10.1016/j.actphy.2025.100126
二氧化碳催化加氢制二甲醚(DME)通常依赖于含铜金属氧化物/分子筛体系;然而,在反应过程中,铜物种向分子筛的迁移难以避免,这会导致Cu0位点和酸性位点的损失。在本工作中,通过共沉淀法合成了Cu/x%Ga-γ-Al2O3双功能催化剂。Ga以低浓度掺杂到γ-Al2O3晶格中,与表面Cu0物种形成界面活性位点,从而实现CO2加氢制DME。实验研究与DFT计算表明,该催化剂在180 h内保持稳定,且Ga掺杂Cu/γ-Al2O3界面位点对CO2加氢制甲醇和甲醇脱水制DME均表现出催化作用。Ga的掺杂增大了催化剂的比表面积,减小了金属Cu0的粒径,增加了催化剂上的酸性和碱性位点数量,并促进了H2和CO2的吸附。此外,还提出了一种新的DME合成反应路径。本工作去除了传统铜基双功能催化剂中的脱水组分,使两个反应能够在同一活性位点上发生,为新型二甲醚合成双功能催化剂的设计提供了新策略。
【无机化学学报】doi: 10.11862/CJIC.20250184
The residues of Al3+, Ga3+, and In3+ in the environment pose an increasingly serious threat to human health and ecosystems. However, their specific and rapid detection remains challenging. In this study, we present a water-stable cadmium metal-organic framework (Cd-MOF) based luminescence probe, which can detect Al3+, Ga3+, and In3+ ions in aqueous solutions via a luminescence "turn-on" mode. The corresponding detection limits for the Al3+, Ga3+, and In3+ ions were 2.31, 3.06, and 2.78 μmol·L-1, respectively. This probe operated effectively within a pH range of 3-10 in an all-aqueous environment. Investigations into the detection mechanism revealed that this "turn-on" recognition is attributed to the formation of new structures upon ion interaction.
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