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多组分协同无机功能材料专辑
2024, 40(11):
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综述
多组分锆基金属有机骨架研究进展
何斌, 张浩, 徐琳, 刘阳河, 郎飞帆, 庞建东
2024, 40(11): 2041-2062  doi: 10.11862/CJIC.20240161
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锆基金属有机骨架(Zr-MOFs)具有丰富的结构类型、出色的热稳定性和化学稳定性以及多样化的功能,被认为是最具应用前景的新型晶态多孔骨架材料之一。通过一锅法及合成后修饰法等多种方法可将具有特定功能化官能团的有机配体引入Zr-MOFs体系,进而实现多组分锆基金属有机骨架(MC-Zr-MOFs)的构筑及对Zr-MOFs孔道环境的有效调控。MC-Zr-MOFs被广泛应用于气体吸附与分离、溶液相客体分子/离子吸附、多相催化、化学传感及光学材料等领域,展现出优异的性能。本文详细梳理了MC-Zr-MOFs的合成策略和应用研究的近期进展,并对其未来发展前景进行了展望。
多组分二维共轭金属有机骨架的研究进展
霍然, 张兆辉, 苏熹, 陈龙
2024, 40(11): 2063-2074  doi: 10.11862/CJIC.20240195
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多组分二维共轭金属有机骨架(MTV 2Dc-MOFs)是一类由多种有机配体和金属节点通过配位键周期性组装而成的新型多孔晶态材料,由于具有可预测的拓扑结构、可调的孔隙率、高电导率和高电催化活性等优点,受到了广泛关注。同时,利用多金属离子或有机配体之间的协同作用,可以有效调节材料的电化学活性和选择性,为制备新型的功能性更强的2D c-MOFs提供了新的思路和方向。在这篇短综述中,我们小结了近年来报道的具有多金属节点或有机配体构建的MTV 2D c-MOFs的研究进展,并对其设计策略(双组分和三组分)、骨架优势和面临的挑战做出了展望。
基于发光铜纳米团簇的多组分体系的构成及应用
黄燕婷, 向华, 潘梅
2024, 40(11): 2075-2090  doi: 10.11862/CJIC.20240196
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铜纳米团簇(copper nanoclusters, Cu NCs)具有独特而优异的光物理性质,近年来在发光领域取得了令人瞩目的研究进展。然而,由于铜易氧化,因而难以获得结构稳定、发光强度高的Cu NCs。将Cu NCs与其他组分结合构建多组分体系,是提高稳定性、优化发光性能的可行策略之一。基于Cu NCs构筑的多组分体系,不仅能够有效弥补其缺陷和不足,而且还能实现发光体系的功能多样化,从而有助于促进该发光材料的实际应用。基于此,本文对该领域的研究进行了综述,首先介绍了Cu NCs的基本结构和发光影响因素,进而分类总结了目前发光Cu NCs多组分体系的构成策略及其应用。
手性铱(钌)配合物在不对称催化反应中的应用进展
乔科, 李彦霖, 黄胜利, 杨国昱
2024, 40(11): 2091-2104  doi: 10.11862/CJIC.20240265
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近年来,将手性八面体金属配合物用于不对称催化引起科学家们的广泛关注。手性八面体金属配合物根据配体是否具有手性可划分为手性仅来源于金属中心及手性来源于手性配体和金属中心的八面体金属配合物。本文介绍并归纳了手性环金属铱(Ir)和钌(Ru)配合物的设计与合成方法,即通过改变金属中心、配体的结合以及配体构型等对其进行调控。随后详细阐述了其在不对称催化中的应用,并根据催化方式不同将应用分为金属配位催化和配体球调控催化。金属配位催化包括多种有机不对称催化,以及可见光诱导多功能催化剂协同不对称催化。配体球调控催化主要用于烯烃加成反应。最后对手性八面体配合物作为配位超分子的建筑单元及其在不对称催化中的应用进行了展望,将二者优势结合有望实现更广泛的应用前景。
从制备到应用:InP量子点的发展与应用前景
苏雨, 范新莲, 殷垚, 王琳
2024, 40(11): 2105-2123  doi: 10.11862/CJIC.20240126
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量子点材料具有与尺寸相关的优异光学性能,如发光波长可谐调、发射半峰宽窄、激发范围宽等,应用领域广泛。然而目前主流的量子点普遍含有镉、铅等元素,不利于商业化产品发展。磷化铟(InP)量子点无重金属毒性,光谱范围可覆盖整个可见光区,具有与镉基量子点相媲美的发光和光电性能,逐渐得到关注。本文综述了近年来InP量子点的合成方法和应用方面的研究进展,首先探讨了热注入、加热、晶核生长、阳离子交换等InP量子点合成方法的优势与缺陷,然后重点介绍了目前InP量子点在照明显示、光伏、光催化和光学标记成像等领域取得的应用成果。最后,从材料合成和器件应用2个角度提出了InP量子点发展面临的挑战及可能的解决方案,以期推动InP量子点的研究和应用,为光电领域的发展提供新的思路。
论文
含四烯基吡啶配体的Zn(Ⅱ)配位聚合物的合成、结构及其荧光性质
桑笑, 刘琦, 郎建平
2024, 40(11): 2124-2132  doi: 10.11862/CJIC.20240158
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在3,5‐二硝基苯甲酸(3,5‐HDNBA)、4‐吡唑羧酸(4‐H2PyC)或对乙基苯甲酸(4‐HEBA)存在下,Zn(NO3)2·6H2O与1,2,4,5‐四(4‐乙烯基吡啶基)苯(tkpvb)发生溶剂热反应,制备了[Zn(tkpvb)(3,5‐DNBA)2]n (CP1)、{[Zn(tkpvb)(4‐PyC)]·2H2O]}n (CP2)和{[Zn(tkpvb)0.5(4‐EBA)2]·H2O}n (CP3)三种Zn(Ⅱ)基配位聚合物(CPs)。通过红外光谱、元素分析、粉末X射线衍射和单晶X射线衍射对它们进行了结构表征。CP1具有一维“之”字形链状结构,CP2CP3则分别呈现六连接和四连接的三维拓扑结构。CP1~CP3均表现出光致发光现象,对无机金属离子有一定的响应性能。其中,Fe3+离子对CP1的荧光强度影响最大,检测限达到0.020 μmol·L-1。这可能是Fe3+CP1中不配位的吡啶基之间的相互作用引起的。
CaCl2@MOF-808原位复合成型颗粒的制备及其集水性能
亢紫亮, 张佳敏, 安虹, 刘小华, 陈杨, 李晋平, 李立博
2024, 40(11): 2133-2140  doi: 10.11862/CJIC.20240282
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将吸湿盐与金属有机骨架(MOF)材料结合,采用原位改性成型方法快速制备吸湿盐负载的CaCl2@MOF‐808复合成型颗粒。基于MOF‐808的高孔隙率和高比表面积,CaCl2可分散在MOF‐808的孔道内,水分子在丰富孔隙环境和吸湿盐的共同作用下被吸附,提升了该成型颗粒在低压下的集水能力。通过X射线粉末衍射、扫描电镜、N2吸附-脱附和吸水测试等表征技术观察成型颗粒的物相及性能,结果表明CaCl2@MOF‐808成型吸附剂机械强度达25 N,满足应用的抗压水平,同时在25 ℃和相对湿度(RH)30%下其吸水率达到最大值0.43 g·g-1,是原始MOF‐808的5倍,具有良好的吸水能力。
泡沫镍负载Co9S8/Ni3S2异质结电催化解耦尿素溶液制氢
郭浩, 韦童, 申晴晴, 洪安琪, 邓泽婷, 方政, 史吉超, 李仁宏
2024, 40(11): 2141-2154  doi: 10.11862/CJIC.20240085
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采用一步水热法合成泡沫镍(NF)自支撑的Co9S8/Ni3S2@NF杂化纳米棒阵列,其可以作为尿素氧化反应(UOR)和析氢反应(HER)的双功能催化剂。物相分析、形貌表征和电化学测试结果表明Co9S8/Ni3S2@NF异质结杂化纳米棒阵列通过Co9S8与Ni3S2之间的耦合异质界面促进了电子转移,提高了电荷转移速率。同时,该催化剂的粗糙表面使其展示出优异的超亲水性和超疏气性,有利于气体输送以及电解液扩散。在UOR和HER中,该催化剂分别在120和103 mV的低过电位下就能达到100和10mA·cm-2的电流密度。此外,利用合成的Co9S8/Ni3S2@NF电极同时作为阴极和阳极,当电流密度达到100 mA·cm-2时双电极电解池的运行仅需要1.57 V的低电压,并且在20 mA·cm-2电流密度下稳定运行27 h,无明显活性衰减。
h-MoO3/SiO2催化合成季戊四醇异辛酸酯
谭益凤, 曹平, 马楷, 李金桐, 王雨恒
2024, 40(11): 2155-2162  doi: 10.11862/CJIC.20240147
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采用固相研磨法,制备了一系列h-MoO3/SiO2催化剂,这些催化剂用于季戊四醇(PER)和异辛酸(i-EHA)反应,合成季戊四醇异辛酸酯(POE),并采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、X射线光电子能谱(XPS)、N2吸附-脱附、扫描电镜(SEM)、透射电镜(TEM)对催化剂进行表征测试。结果表明,h-MoO3负载量为15%的(200)晶面择优取向的h-MoO3/SiO2是合成POE的优良催化剂。适宜的反应工艺条件(ni-EHA/nPER=4.3,mh-MoO3/SiO2/mPER=0.003,T=220℃,t=4 h)下,酯化率可达90.83%,POE的选择性可达100%。
改进共沉淀法制备高比表面积钒酸镍负极材料及其电化学性能
张宇婷, 刘尊义, 李宁, 张栋强, 赵仕玲, 赵鹬
2024, 40(11): 2163-2174  doi: 10.11862/CJIC.20240204
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以去离子水为绿色溶剂,Ni (NO3)2·6H2O为镍源,NH4VO3为钒源,通过碳酸钠溶液调节沉淀pH值,正丁醇干燥提高比表面积及颗粒分散度,采用改进的共沉淀法制备了相对廉价的钒酸镍负极材料(NVO-NBA)。通过对其微观形貌、比表面积、孔径大小及表面元素分布进行测试,探究了改进共沉淀法对钒酸镍电极材料织构性质的影响。结果表明,沉淀过程中溶液pH值的精准调节及后续加入表面张力较小的醇类溶剂的干燥方式对材料的比表面积、孔径大小、微观结构及颗粒分散度有显著的影响,其中在pH=8的条件下沉淀、后续加入正丁醇辅助干燥得到的样品NVO-8-NBA具有最大的比表面积(86 m2·g-1),同时材料形貌为分散度较高、直径较小的球形纳米颗粒。加入乙醇、正丁醇、正己醇等醇类溶剂进行后续干燥得到的钒酸盐材料比表面积均比未加醇处理的样品显著提高,而正丁醇处理的样品效果最好,表明表面张力较小的醇类溶剂可以有效保护共沉淀过程生成的孔道体系,并可使颗粒分散更均匀,同时醇类的碳链长度对其性质也具有显著的影响。未加醇处理的样品NVO-8比表面积仅为20 m2·g-1,形貌为聚集的大块状。将制备的钒酸镍材料作为锂离子电池的负极材料,其在0.3 A·g-1的电流密度下,NVO-8-NBA的首圈放电容量可以达到1 519 mAh·g-1,而NVO-8仅为536 mAh·g-1。NVO-8-NBA在0.3 A·g-1的电流密度下循环100次后容量保持在223 mAh·g-1,而NVO-8仅为70 mAh·g-1且仍有继续下降的趋势。
基于限阈空间制备Mn单原子催化剂及其电催化析氧性能
王洋, 郑晓芹, 刘洋, 张凯, 寇佳慧, 孙林兵
2024, 40(11): 2175-2185  doi: 10.11862/CJIC.20240165
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采用一种简单的策略,以未去除模板剂的原粉介孔二氧化硅KIT-6(TOK)为载体,利用模板剂和二氧化硅壁之间的限阈空间来制备单原子催化剂(SACs)。通过固相研磨将含Mn前驱体引入TOK的固有限阈空间后,Mn SACs可在热处理过程中迅速生成。密度泛函理论计算和实验数据表明,Mn原子被载体上的Si—OH基团所锚定,并以Mn—O—Si的形式存在。将得到的Mn SACs应用于电催化析氧反应,实验结果显示,与在没有限阈空间载体中合成的对比样品相比,Mn SACs表现出更出色的催化性能。
Articles
Synthesis and structures of cdq-topological quaternary and (4, 4, 8)-c topological quinary Zn-MOFs with both oxalic acid and triazole ligands
Jing LIANG, Qian WANG, Junfeng BAI
2024, 40(11): 2186-2192  doi: 10.11862/CJIC.20240177
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Different solvothermal reactions of ZnC2O4 with oxalic acid (H2ox) and 1, 2, 4-triazole (Htrz) successfully gave a new quaternary (NJTU-Bai83, NJTU-Bai=Nanjing Tech University Bai's group) and a new quinary (NJTU- Bai84) anionic metal-organic frameworks (MOFs), where NJTU-Bai83=(Me2NH2)2[Zn3(trz)2(ox)3]·2H2O and NJTU-Bai84=(Me2NH2)[Zn3(trz)3(ox)2]·H2O, respectively. With the [Zn2(ox)4(trz)2] secondary building unit (SBU) in NJTU- Bai83 replaced by the [Zn3(ox)2(trz)6] and planar [Zn(ox)2(trz)2] ones in NJTU-Bai84, 2D supramolecular building layers (SBLs) are changed from the A-layer and B-layer to another A-layer, while pillars are transformed from the tetrahedral [Zn(ox)2(trz)2] SBU to the irregular tetrahedral [Zn(ox)2(trz)2] and planar [Zn(ox)2(trz)2] SBUs. Thus, cdq-topological quaternary NJTU-Bai83 is tuned to (4, 4, 8)-c new topological quinary NJTU-Bai84. Two MOFs were well characterized by powder X-ray diffraction, thermogravimetric analysis, elemental analysis, etc.
Electro-copolymerized film of ruthenium catalyst and redox mediator for electrocatalytic water oxidation
Hao WANG, Kun TANG, Jiangyang SHAO, Kezhi WANG, Yuwu ZHONG
2024, 40(11): 2193-2202  doi: 10.11862/CJIC.20240176
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Electro-copolymerized film containing ruthenium complexes as electron-transfer (or redox) mediators and water-oxidation catalysts by an oxidative copolymerization method is presented. The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV. The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s-1 and an initial turnover frequency of 1.01 s-1 in 1 000 s by potential electrolysis at 1.7 V applied bias vs NHE (normal hydrogen electrode). The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.
Effects of anions on the structural regulation of Zn-salen-modified metal-organic cage
Qiaojia GUO, Junkai CAI, Chunying DUAN
2024, 40(11): 2203-2211  doi: 10.11862/CJIC.20240209
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By virtue of a 3∶1 complementary coordination strategy, a chiral heteroleptic metal-organic cage that contains divergent functional units, Pd-R(Zn), was precisely constructed via self-assembly of monodentate variational Znsalen ligands RZn and NADH (reduced nicotinamide adenine dinucleotide) mimic modified tridentate ligands with square-planar Pd ions. UV-Vis and luminescence spectra experiments reveal that different anions could selectively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound, by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts. Compared to other anions, the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd-R(Zn), meanwhile, the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease, and the metal-to-ligand induced peak displayed a blue shift effect. Circular dichroism and 1H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.
Structures and magnetism of dinuclear Co complexes based on imine derivatives
Yadan SUN, Xinfeng LI, Qiang LIU, Oshio Hiroki, Yinshan MENG
2024, 40(11): 2212-2220  doi: 10.11862/CJIC.20240131
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This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives: bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether (L1), bis-[4-(2-pyridylmethyleneamino)-phenyl]ether (L2), and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane (L3). Single-crystal X-ray diffraction analysis reveals that the complexes [Co2(L1)3](ClO4)4·2CH3CN (1), [Co2(L2)3](ClO4)4·2CH3OH (2), and [Co2(L3)3](ClO4)4·2CH3OH (3) all exhibit a dinuclear structure. Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K, with the average Co—N bond length increasing from 0.213 9(3) to 0.215 3(3) nm. Meanwhile, the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2. Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.
Transition metal coordination polymers with flexible dicarboxylate ligand: Synthesis, characterization, and photoluminescence property
Peipei CUI, Xin LI, Yilin CHEN, Zhilin CHENG, Feiyan GAO, Xu GUO, Wenning YAN, Yuchen DENG
2024, 40(11): 2221-2231  doi: 10.11862/CJIC.20240234
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Under solvothermal conditions, six new coordination polymers (CPs) [Mn(L) (phen) (H2O)]n (1), [Co(L) (phen)(H2O)]n (2), [Cu(L)(phen)(H2O)]n (3), [Zn2(L)2(phen)2(H2O)]n (4), [Zn(L)(phen)]n (5), and [Cd(L)(phen)2]n (6) were synthesized by reactions of dicarboxylate ligand 2, 2'-(1, 2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid (H2L) and 1, 10-phenanthroline (phen) with the corresponding metal salts. Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, IR, thermogravimetric analysis, and powder X-ray diffraction. The structures of 1-6 are 1D chains, which are further connected by hydrogen bonding interactions to form 3D supramolecular structures. Among them, 1 and 2 are isomorphic with L2- of syn-conformation, while L2- shows anti-conformation in 3-6. In addition, the solid-state photoluminescence property of 4-6 was investigated.
Co3O4/TiO2 composite photocatalyst: Preparation and synergistic degradation performance of toluene
Fei ZHOU, Xiaolin JIA
2024, 40(11): 2232-2240  doi: 10.11862/CJIC.20240236
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摘要:
TiO2 nanobelts and Co3O4/TiO2 catalytic materials were prepared using the hydrothermal method. The catalyst was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray electron spectroscopy, and fluorescence spectroscopy. At room temperature, with a relative humidity of 50.0%, the total gas flow rate of 1.0 L·min-1, the space velocity of 1.05×104 h-1, and toluene volume concentration of 25.0 μL·L-1, two 6 W vacuum ultraviolet lamps were used as light sources to catalyze, degrade, and mineralize toluene. The results show that the prepared catalyst is in the shape of nano-ribbons. The loading of Co3O4 inhibits the recombination of photogenerated electrons and holes and can effectively improve the catalytic performance. The Co3O4/TiO2 with a load of 6.0% Co3O4 has the best catalytic effect. When N2 was used as a carrier gas, the degradation rate of toluene was only 34.7%. The toluene degradation is mainly due to the photolysis of vacuum ultraviolet light. When air was used as a carrier gas, O3 was produced. The Co3O4/TiO2 with a load of 6.0% and vacuum ultraviolet synergistically promote toluene degradation. The highest degradation rate of toluene was 91.7% and the mineralization rate was 74.6%. The degradation rate of toluene was 2.6 times that of nitrogen as a carrier gas.
Construction and photocatalytic properties toward rhodamine B of CdS/Fe3O4 heterojunction
Yuan CONG, Yunhao WANG, Wanping LI, Zhicheng ZHANG, Shuo LIU, Huiyuan GUO, Hongyu YUAN, Zhiping ZHOU
2024, 40(11): 2241-2249  doi: 10.11862/CJIC.20240219
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摘要:
A simple two-step hydrothermal method synthesized four different CdS/Fe3O4 photocatalysts with varying ratios of mass of CdS to Fe3O4. The composition and morphology of the prepared samples were investigated using X-ray diffraction (XRD), Raman spectrum, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Solid UV reflectance spectra testing found that CdS/Fe3O4 nanocomposites had good light absorption throughout the spectral range, promoting their photocatalytic properties. Under visible light irradiation, CdS/Fe3O4 (2:5) with a mass ratio of 2:5 exhibited excellent photocatalytic performance, with a degradation rate of 98.8% for rhodamine B. Furthermore, after five cycles of photocatalytic degradation reaction, the rhodamine B degradation rate remained at 96.2%, indicating that the photocatalysts have good photocatalytic stability.
First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe
Shenhao QIU, Qingquan XIAO, Huazhu TANG, Quan XIE
2024, 40(11): 2250-2258  doi: 10.11862/CJIC.20240104
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摘要:
The electronic structure, magnetic, and optical properties of two-dimensional(2D) GaSe doped with rare earth elements X (X=Sc, Y, La, Ce, Eu) were calculated using the first-principles plane wave method based on density functional theory. The results show that intrinsic 2D GaSe is a p-type nonmagnetic semiconductor with an indirect bandgap of 2.661 1 eV. The spin-up and spin-down channels of Sc-, Y-, and La-doped 2D GaSe are symmetric, they are non-magnetic semiconductors. The magnetic moments of Ce- and Eu- doped 2D GaSe are 0.908μB and 7.163μB, which are magnetic semiconductors. Impurity energy levels appear in both spin-up and spin-down channels of Eu-doped 2D GaSe, which enhances the probability of electron transition. Compared with intrinsic 2D GaSe, the static dielectric constant of the doped 2D GaSe increases, and the polarization ability is strengthened. The absorption spectrum of the doped 2D GaSe shifts in the low-energy direction, and the red-shift phenomenon occurs, which extends the absorption spectral range. The optical reflection coefficient of the doped 2D GaSe is improved in the low energy region, and the improvement of Eu-doped 2D GaSe is the most obvious.
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Articles
Self-assembly of [Pd6(L)4]8+-type macrocyclic complexes for fluorescent sensing of HSO3-
Xiaofei NIU, Ke WANG, Fengyan SONG, Shuyan YU
2024, 40(7): 1233-1242  doi: 10.11862/CJIC.20240057
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摘要:
In this study, parallelogram-like macrocyclic supramolecular metallacycles [Pd6(bpy)6(L1)4](PF6)8 (1a) and [Pd6(bpy)6(L2)4](PF6)8 (2a), where HL1=1-(1H-pyrazole-4-yl)-4-(4-pyridyl)benzene, HL2=9-(1H-pyrazole-4-yl)-10-(4-pyridyl)anthracene, and bpy=2, 2'-bipyridine, are synthesized by reacting aryl pyrazole pyridine ligands with dipalla-dium corners in aqueous solutions via metal-directed hierarchical self-assembly. The structures of the supramolecular Pd parallelograms are confirmed through single-crystal X-ray diffraction. Notably, the two parallelogram metallacycles can be used as"turn-on"fluorescence sensors to detect HSO3- through a disassembly mechanism. In addition, the 1a-based sensor shows selective detection of HSO3- without interference from other anions. The detection limit was as low as 0.131 μmol·L-1. Furthermore, complex 1a presented the semiquantitative visual detection ability for HSO3- in the test trip mode via fluorescence changes.
Syntheses, structures, photochromic and photocatalytic properties of two viologen-polyoxometalate hybrid materials
Huirong LIU, Hao XU, Dunru ZHU, Junyong ZHANG, Chunhua GONG, Jingli XIE
2024, 40(7): 1368-1376  doi: 10.11862/CJIC.20240066
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摘要:
Two new viologen-polyoxometalate hybrid crystalline materials: (MV)2[HPW2W10O40] ·2H2O (1) and (EV)2[Mo8O26] (2) have been synthesized by using the cations of 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (methyl viologen, MV) and 1, 1'-diethyl-4, 4'-bipyridinium dibromide (ethyl viologen, EV) as the electron acceptors, and the electron-rich polyoxometalate anions as the electron donors. The structures of compounds 1 and 2 have been determined by single-crystal X-ray crystallography. Hydrogen bond interactions exist between the cations and the anions in 1 and 2. Interestingly, 2 has a photochromic performance with a light response time within 1 min. The photochromic mechanism of compound 2 has been investigated by solid-state diffuse reflection, electron paramagnetic resonance and theoretical calculation. 1 and 2 show good catalytic performance in the photocatalytic degradation of several organic dyes (methylene blue, pararosaniline hydrochloride and rhodamine 6G).
Construction of two metal-organic frameworks by rigid bis(triazole) and carboxylate mixed-ligands and their catalytic properties for CO2 cycloaddition reaction
Weichen WANG, Chunhua GONG, Junyong ZHANG, Yanfeng BI, Hao XU, Jingli XIE
2024, 40(7): 1377-1386  doi: 10.11862/CJIC.20230415
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Two metal-organic frameworks (MOFs) containing rigid bis(triazole) ligand, namely {[Zn2(L)(TP)2(H2O)·H2O]}n (1) and [Zn(L)(HTMA)]n (2), where L=4, 4'-(3, 3'-dimethyl-(1, 1'-biphenyl)-4, 4'-diyl)bis(4H-1, 2, 4-triazole), H2TP=terephthalic acid, H3TMA=1, 3, 5-benzenetricarboxylic acid, were synthesized by using acid-base mixed ligands strategy and structurally characterized by X-ray single-crystal diffraction. Structural analysis reveals that MOF 1 displays a 3, 6-connected 2D structure with a new topological point symbol of (42·6)2(48·66·8), while MOF 2 presents a 2D sql topology structure. The catalytic studies reveal that 2 exhibits excellent catalytic activity for the cycloaddition reaction of CO2 with epoxides under mild conditions. Furthermore, 2 can be reused at least three times while maintaining its catalytic ability.
A(NH2SO3) (A=Li, Na): Two ultraviolet transparent sulfamates exhibiting second harmonic generation response
Cuiwu MO, Gangmin ZHANG, Chao WU, Zhipeng HUANG, Chi ZHANG
2024, 40(7): 1387-1396  doi: 10.11862/CJIC.20240045
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摘要:
Two alkali-metal sulfamates nonlinear optical (NLO) crystals, Li(NH2SO3) and Na(NH2SO3), have been obtained through the facile evaporation method. Li(NH2SO3) crystallizes in the polar space group Pca21 (No.29). The structure of Li(NH2SO3) can be described as a 3D network formed by [LiO4]7- polyhedral connecting with NH2SO3- tetrahedra through corner-sharing. Na(NH2SO3) crystallizes in the polar space group P212121 (No.19). The structure of Na(NH2SO3) can be described as a 3D network formed by distorted [NaO6]11- octahedral connecting with NH2SO3- tetrahedra through corner-sharing. The UV-Vis-near-infrared spectra demonstrate that Li(NH2SO3) and Na(NH2SO3) possessed large optical band gaps of 5.25 and 4.81 eV, respectively. Powder second-harmonic generation (SHG) measurements demonstrate that the SHG intensity of Li(NH2SO3) and Na(NH2SO3) were 0.32 times and 0.31 times that of KH2PO4, respectively. First-principles calculations confirm the nonlinear optical performance mainly derived from the synergistic effect of amino sulfonate anions and alkali metal oxide anionic polyhedra.
Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid
Kaimin WANG, Xiong GU, Na DENG, Hongmei YU, Yanqin YE, Yulu MA
2024, 40(7): 1397-1408  doi: 10.11862/CJIC.20240009
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5-(dimethylamino) isophthalic acid (H2dia) and 1H-imidazole (mdz) were used as ligands to react with Zn(Ⅱ) or Cu(Ⅱ) metal salts to generate three new transition metal complexes [Zn(dia)(mdz)2]·2H2O (1), [Cu(dia)(mdz)2 (DMF)] (2) and [Cu(dia)(mdz)2]·H2O (3). Their structures were characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analyses, and Hirshfeld surface analyses. The results revealed that complexes 1 and 2 possess 1D linear chains, each four-coordinated Zn(Ⅱ) of 1 is located in the geometric center of the distorted tetrahedron, but the Cu(Ⅱ) metal center of 2 is five-coordinated and holds a triangular bipyramidal geometry. The zigzag 1D chain of complex 3 was obtained by changing the solvent in the synthesis, and the four-coordinated Cu(Ⅱ) ion is in the centre of the square planar. Results indicate that the geometries of metal centers and synthetic solvents have important effects on the structures of complexes. Abundant intermolecular hydrogen bonding plays an important role in the stability of their 3D supramolecular structures. Thermogravimetric analyses revealed that the complexes have good thermal stabilities. Solid fluorescence analyses showed that complex 1 had excellent fluorescence, but the fluorescence intensities of complexes 2 and 3 were much lower than those of ligands.
Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands
Maitri Bhattacharjee, Rekha Boruah Smriti, R. N. Dutta Purkayastha, Waldemar Maniukiewicz, Shubhamoy Chowdhury, Debasish Maiti, Tamanna Akhtar
2024, 40(7): 1409-1422  doi: 10.11862/CJIC.20240007
[摘要]  (363) [HTML全文] (363) [PDF 10357KB] (363)
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Three new copper(Ⅱ) complexes 1-3 of Schiff base ligands HL1 (2-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone), HL2 (4-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) and L3 (2-methoxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) were synthesized from methanolic medium. The complexes were characterized by elemental analyses, spectroscopic methods, magnetic susceptibility measurements, and density functional theory (DFT) studies. The synthesized ligands were characterized structurally by single-crystal X-ray diffraction studies. The optimized structure of the complexes was ascertained by DFT studies. The DNA binding ability of the complexes with calf thymus DNA (CT-DNA) was studied by UV-Vis absorption and fluorescence emission spectral studies. Absorption spectral studies revealed a hyperchromic effect and suggested the possible mode of interaction with CT-DNA. The competitive binding studies using ethidium bromide (EB) show that the complexes can replace DNA from DNA-EB adduct and suggests that the complexes probably bind to CT-DNA in intercalative mode. In vitro antibacterial activity of the complexes against Gram-negative bacteria Klebsiella pneumoniae (K. pneumoniae), Escherichia coli(E. coli), and Shigella boydii (S. boydii), and gram-positive bacteria Staphylococcus aureus (S. aureus) exhibited an appreciable antibacterial activity of complex 2 against K. pneumoniae and S. boydii, but complexes 1 and 3 did not show any significant antibacterial activity.
论文
基于有机溶剂原位制备的致密疏水铜金属层在保护锌负极中的应用
罗秋洋, 唐晓宁, 夏澍, 刘珺楠, 杨兴富, 雷杰
2024, 40(7): 1243-1253  doi: 10.11862/CJIC.20240110
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摘要:
通过在N-甲基吡咯烷酮(NMP)有机溶剂中锌电极与CuI之间的置换反应,在锌电极上原位构建了一层致密且疏水的铜金属保护层(Cu@Zn)。铜金属保护层能有效地隔离锌电极与电解液的接触,减少锌电极-电解液界面的析氢和腐蚀等副反应。同时,铜金属保护层还具有较好的亲锌性,更小的界面电阻,更低的成核能垒,有利于锌离子均匀沉积,从而有效抑制了锌枝晶的生成。Cu@Zn对称电池实现了超过1 700 h(1 mA·cm-2)和1 330 h(3 mA·cm-2)的循环寿命。采用商用MnO2与之匹配得到的Cu@Zn||MnO2全电池不仅在1 A·g-1下具有168.5 mAh·g-1的可逆比容量,还可稳定循环2 000次以上
Cu掺杂对Au11(dppf)4Cl2纳米团簇结构和光学性质的影响
周鹏, 蔡潇, 马清祥, 刘旭
2024, 40(7): 1254-1260  doi: 10.11862/CJIC.20240047
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摘要:
通过一锅还原法成功制备了合金纳米团簇Au11-xCux(dppf)4Cl2(x=1、2;dppf=1,1'-双(二苯基膦)二茂铁)。晶体结构解析表明,合金团簇具有与Au11(dppf)4Cl2类似的几何结构,如含有缺陷二十面体金属内核,不同之处在于Cu原子取代了与Cl配位的Au原子。因此,Au11-xCux(dppf)4Cl2可视为Cu对Au11(dppf)4Cl2模板团簇的掺杂。Cu原子的引入并未改变模板团簇Au11(dppf)4Cl2的框架结构,但有效调控了电子结构,进而使其光吸收发生红移。
分级中空结构BiOBr-Pt催化剂用于光催化CO2还原
王坤, 刘文蕊, 江鹏, 宋宇航, 陈丽华, 邓兆
2024, 40(7): 1270-1278  doi: 10.11862/CJIC.20240037
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摘要:
以乙二醇为溶剂,聚乙烯吡咯烷酮为表面活性剂,通过一步溶剂热法合成了分级中空结构的BiOBr-Pt催化剂。合成的分级中空结构BiOBr-2h催化剂的比表面积为28 m2·g-1,是对比样品BiOBr-1h的2倍,这种结构为催化反应提供更多的反应活性位点。此外,在催化剂中引入Pt增强了BiOBr的载流子传导速率,而且Pt可以作为电子陷阱捕获周围大量电子,有效抑制光生载流子的复合,从而提高CO2还原的催化活性。光催化CO2还原实验结果表明,BiOBr-Pt的主要产物为CO,产物选择性为99%,其CO产率达到了20.8 μmol·h-1·g-1,为原始BiOBr的2.1倍。这一结果说明,这种Pt负载且具有分级中空结构的催化剂可以有效地将CO2转化为增值化学品。
高硅ZSM-5沸石孔道和酸性的协同调控及其催化甲醇制丙烯反应性能
李兴扬, 刘田菊, 高阳, 张丹丹, 周勇, 潘梦
2024, 40(7): 1279-1289  doi: 10.11862/CJIC.20240026
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通过碱处理结合铬改性策略实现了对高硅ZSM-5沸石孔道和酸性的协同调控,制备出了一种具有适宜酸性的高硅多级孔沸石催化剂。在碱处理的过程中,通过精细调节合成凝胶组成,在沸石晶体中引入的丰富共生界面,诱导了介孔的形成,从而打破了沸石硅铝比对常规碱处理法的限制。在铬改性的过程中,独特的多级孔结构促进了铬在催化剂中的分散,从而实现了对酸性的深度改性。在甲醇制丙烯催化反应中,制备的催化剂表现出了极佳的催化稳定性以及很高的丙烯和总低碳烯烃选择性。
I2界面修饰对全无机CsPbBr3钙钛矿太阳能电池性能的影响
王则远, 郑松志, 李浩, 翁敬菠, 王威, 汪杨, 孙伟海
2024, 40(7): 1290-1300  doi: 10.11862/CJIC.20240021
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通过在CsPbBr3薄膜上旋涂一次I2的异丙醇溶液以修饰CsPbBr3吸光层,钝化CsPbBr3层表面缺陷,改善CsPbBr3薄膜形貌。同时通过利用环境友好的绿色溶剂水溶解CsBr,显著提高了其溶解度,减少了旋涂次数,简化了电池制备流程。实验结果表明,在CsPbBr3钙钛矿太阳能电池(perovskite solar cells,PSCs)中,使用5 mg·mL-1 I2的异丙醇溶液界面修饰的器件具有最佳光伏性能,其最高开路电压(open-circuit voltage,VOC)为1.55 V,短路电流密度(short circuit current density,JSC)为7.45 mA·cm-2,填充因子(fill factor,FF)为85.54%,光电转换效率(photoelectric conversion efficiency,PCE)达到了9.88%。
两个丁二肟有机锡配合物的合成、结构及抗癌活性
卿菁菁, 何帆, 刘智辉, 侯帅鹏, 刘娅, 蒋一凡, 谭梦婷, 何丽芳, 张复兴, 朱小明
2024, 40(7): 1301-1308  doi: 10.11862/CJIC.20240003
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合成了2个丁二酮肟有机锡化合物:双(三(2-甲基-2-苯基丙基)锡)丁二酮肟配合物(C6H5C(CH3)2CH2)3Sn(ON=C(CH3)C(CH3)=NO)Sn(CH2C(CH3)2C6H5)3 (1)和二苄基锡氧氯丁二酮肟多核配合物[μ3-O-((C6H5CH2)2Sn)2(ON=C(CH3)C(CH3)=NOH)(O)Cl]2(2)。通过元素分析、红外光谱、核磁共振(1H、13C、119Sn)、差热分析和单晶X射线衍射对配合物进行了结构表征,对其结构进行量子化学从头计算,并进行了体外抗癌活性研究。结果显示:配合物1为通过配体丁二酮肟桥联的双锡核中心对称分子,锡原子均为四配位的畸变四面体构型;配合物2为通过氧原子和丁二酮肟配体桥联的四锡核中心对称多环聚合结构,锡原子分别为五配位的畸变三角双锥构型和六配位的畸变八面体构型。配合物对人肝癌细胞(HUH7)、人肺癌细胞(A549)、人表皮癌细胞(A431)、人结肠癌细胞(HCT-116)和人乳腺癌细胞(MDA-MB-231)均有较强的抑制活性。
Cu2O/Cu-垂直石墨烯微电极的制备及尿酸/脑电的检测
白浩, 冀伟志, 陈瑾妍, 李红姬, 李明吉
2024, 40(7): 1309-1319  doi: 10.11862/CJIC.20240001
[摘要]  (338) [HTML全文] (338) [PDF 29658KB] (338)
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结合Cu(Ⅱ)离子浸渍吸附方法及直流电弧等离子体喷射化学气相沉积技术制备了一种电化学/电生理双模Cu2O/Cu-垂直石墨烯微电极,并研究了电化学方法检测尿酸以及记录脑电信号的双响应性能。使用扫描电子显微镜、透射电子显微镜、X射线衍射仪表征了形貌、微结构及晶体成分,并测试了电化学及脑电记录能力。结果表明,该微电极直径仅为200 μm,大量镶嵌Cu2O/Cu纳米粒子的石墨烯纳米片垂直生长在基片上,排列成了一种三维的多孔结构,使其具有了高的电化学催化活性、短程离子扩散路径、以及长程导电网络。由此,以10 μL的饱和NaCl溶液为介质记录脑电信号时,该微电极的皮肤接触电阻低至约7.05 kΩ,生理电采集性能接近涂导电膏的商用湿电极。此外,该微电极还灵敏响应尿酸的氧化电流,检测浓度范围在0.5~500μmol·L-1,检测限低至0.024 μmol·L-1,且具有良好的抗干扰能力及长期稳定性。
Y(PO3)3双包覆改性对Li[Ni0.8Co0.15Al0.05]O2电化学性能的影响
李泓漪, 吴爱民, 赵刘洋, 刘新朋, 陈凤琴, 李爱魁, 黄昊
2024, 40(7): 1320-1328  doi: 10.11862/CJIC.20230480
[摘要]  (426) [HTML全文] (426) [PDF 31881KB] (426)
摘要:
在镍钴铝酸锂正极材料Li[Ni0.8Co0.15Al0.05]O2(NCA)制备过程中表面遗留的碱性物质会严重影响其循环稳定性能,针对这一难题,提出使用Y(PO3)3对其进行表面包覆改性,利用Y(PO3)3与表面残留的LiOH反应消除表面残碱,并探讨包覆改性对NCA整体性能的影响机制。测试分析结果表明,在低温煅烧过程中前驱体表面会形成均匀致密的Y(PO3)3和LiPO3包覆层,LiPO3有较高的离子电导率,双包覆层能够防止活性物质在电化学循环过程中与电解液相互接触时发生有害副反应,提高电极材料的循环稳定性。其中Y(PO3)3包覆量(质量分数)为1%的样品在0.1C下的首次库仑效率从未改性样品的78.65%提高到88.50%,在1C下循环150圈后容量保持率从59.38%提高到85.33%,相比于未改性样品具有更高的首次库仑效率和更优异的循环性能。
氧化石墨烯浓度对还原氧化石墨烯/ZnS电化学性能的影响
徐志环, 康晴, 龙玉珍, 袁倩, 刘次东, 李信, 唐耿怀, 廖雨清
2024, 40(7): 1329-1336  doi: 10.11862/CJIC.20230447
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摘要:
以氧化石墨烯(GO)、乙酸锌(Zn(CH3COO)2)和硫脲为原料,采用水热法成功制备了还原氧化石墨烯/ZnS(rGO/ZnS)复合材料,并将该材料用作锂离子电池负极。高导电性的rGO可以为锂离子和电子的传输提供有效的路径,ZnS可以提供较高的理论比容量。rGO/ZnS复合材料在rGO与纳米级高度分散的类球形ZnS颗粒协同作用下展现了较好的嵌锂容量和循环性能。当GO质量浓度为2 mg·mL-1时制备的rGO/ZnS复合材料的倍率性能最好,循环稳定性最佳。
孔内富氨基的高稳定性铟基金属有机骨架高灵敏电化学传感多巴胺
苏婧, 李冰融, 白乙艳, 籍文娟, 杨海英, 范哲锋
2024, 40(7): 1337-1346  doi: 10.11862/CJIC.20230414
[摘要]  (340) [HTML全文] (340) [PDF 11913KB] (340)
摘要:
为设计高稳定性且高灵敏度的纯金属有机骨架(MOF)电化学传感器以检测多巴胺(DA),我们选用铟基MOF [In(2-NH3-BDC)(2-NH2-BDC)]·1.5H2O(RSMOF-1,RSMOF=resistance switchable metal-organic framework,2-NH2-H2BDC=2-氨基对苯二甲酸)修饰玻碳电极(RSMOF-1/GCE)。制备的电极RSMOF-1/GCE的DPV测试结果显示其线性范围为0.990~663 μmol·L-1、检出限为0.770 μmol·L-1。在多种干扰物质如尿酸、尿素、葡萄糖和对乙酰氨基酚存在的条件下,RSMOF-1/GCE对DA仍具有高的选择性。理论模拟结果显示,在RSMOF-1孔道内壁的—NH2可通过氢键增强与DA分子的相互作用,使RSMOF-1/GCE具有灵敏的电化学传感DA的性能。
一例由多齿席夫碱构筑的Tb2配合物的结构、荧光性质及生物活性
马鑫, 孙娅, 孙楠, 康倩, 张佳佳, 朱瑞涛, 高晓丽
2024, 40(7): 1347-1356  doi: 10.11862/CJIC.20230357
[摘要]  (365) [HTML全文] (365) [PDF 7878KB] (365)
摘要:
使用多齿希夫碱配体H4L(H4L=N',N″-((1E,1'E)-(1,10-菲咯啉-2,9-二酰基)双(亚甲基)双(2-羟基苯甲酰肼))与Tb(acac)3·2H2O反应(acac-=乙酰丙酮根),通过溶剂热法,设计并合成了一例结构新颖的双核铽配合物[Tb2(L)(H2L)]·2CH3OH·CH3CN (1),并研究了该配合物的结构、荧光性质及生物活性。单晶X射线衍射分析表明该配合物主要含有2个Tb离子和2个失去不同质子的配体离子(L4-和H2L2-)。中心Tb1和Tb2离子都是九配位的,其几何构型呈现扭曲的呼啦圈形。固体荧光实验测试结果表明:该配合物在室温下表现出Tb离子的荧光特征发射峰。生物活性研究表明,与配体H4L和稀土离子相比较,配合物具有更强的抗菌活性。采用紫外可见光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了该配合物与小牛胸腺DNA之间的相互作用,结果表明配合物主要以插入作用的方式与小牛胸腺DNA结合。
PtRu/氮掺杂碳电催化甲醇氧化及电解水析氢性能
陈凯, 吴锋顺, 肖顺, 张进宝, 朱丽华
2024, 40(7): 1357-1367  doi: 10.11862/CJIC.20230350
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摘要:
将三聚氰胺、RuCl3及炭黑以一定的比例分散于乙醇中,采用旋转蒸干及高温热处理合成了一种氮掺杂碳(NC)负载Ru的Ru/NC催化剂。采用硼氢化钠液相化学还原法合成了不同Pt、Ru负载量的PtRu/NC催化剂,并用于电催化甲醇氧化反应(MOR)及电催化分解水析氢反应(HER)。结果表明,合成的催化剂中Pt1Ru/NC(Pt、Ru的实际负载量分别为1.14%、0.54%)表现出最优的MOR性能,质量活性达4.96 A·mgPtRu-1,且经10 000 s稳定性测试后质量活性保持在测试前的91.1%。同时,当电流密度为100mA·cm-2时,Pt1Ru/NC在HER中表现出最低的过电位(103 mV)和最小的Tafel斜率(15.29 mV·dec-1)。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、扫描透射电子显微镜(STEM)、电感耦合等离子体发射光谱(ICP-OES)、STEM-能谱(STEM-EDS)技术表征了PtRu/NC双金属催化剂,其具有优异催化性能的原因如下:(1) PtRu双金属纳米颗粒高度分散于NC上;(2) Pt以纳米团簇或单原子形式负载于Ru上,后负载于NC,形成了Pt-Ru相分离结构;(3) Pt、Ru与N之间存在协同效应。