贵金属/ MOFs纳米复合结构材料及其应用进展

郑唯璐; 张洪华; 江龙发; 游奥骐; 唐斯琪

贵金属/ MOFs纳米复合结构材料及其应用进展

1.
江西科技师范大学　材料与能源学院, 江西南昌 330036
2.
南昌海关技术中心, 江西南昌 330038

基金项目: 国家自然科学基金(52063015，51861008)；江西科技师范大学研究生创新专项资金(YC2023-X23)

详细信息

通讯作者:
张洪华，博士，副教授，硕士生导师，研究方向为金属微纳米结构阵列及生化传感应用　E-mail: 15270008537@163.com

中图分类号: TB333
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- 文章访问数: 63
- HTML全文浏览量: 27
- 被引次数: 0
出版历程
- 收稿日期: 2024-04-19
- 修回日期: 2024-05-28
- 录用日期: 2024-05-31
- 网络出版日期: 2024-06-25

Progress in noble metal/ MOFs nanocomposite structure materials and their applications

1.
School of Materials and Engergy, Jiangxi Science and Techonlogy Normal University, Nanchang 330013, China
2.
Technology Center of Nanchang Customs District, Nanchang 330038, China

Funds: National Natural Science Foundation of China (No.52063015, 51861008); Postgraduate Innovation Fund of Jiangxi Science and Technology Normal University (No.YC2023-X23)

摘要

摘要: 金属有机框架(MOFs)由于具有巨大的比表面积、超高的孔隙率、易修饰性和大量的活性位点及多孔结构等特性引起了研究人员的广泛关注，并应用于气体储存、传感器、催化剂等领域。然而，由于其自身固有缺陷，在上述领域实际应用中受到了限制。贵金属纳米材料具有优异的导电性、良好的催化性和独特的LSPR效应等特点，因此，近年来研究人员将贵金属纳米材料与MOFs进行多种形式的精妙组合构筑出纳米复合结构材料，由于二者“协同效应”产生一系列新颖特性，丰富了MOFs材料的应用领域，并显著提高了使用性能。本文综述了近年来Au、Ag、Pt等贵金属/MOFs纳米复合结构材料在催化、传感、生物医学和储氢等领域的应用进展，为制备新的纳米复合结构材料及开拓新的应用提供新思路。
- 金属有机框架 /
- 贵金属 /
- 纳米复合结构 /
- 催化 /
- 传感 /
- 治癌
Abstract: Metal-organic frameworks (MOFs) have attracted much attention due to their large specific surface area, high porosity, easy modification, large number of active sites and porous structures, and have been widely used in many fields, such as gas storage, sensors, catalysts and other fields. However, due to its inherent defects, their further practical applications in the above fields have been limited. Noble metal nanomaterials have excellent electrical conductivity, good catalysis and unique LSPR effect. Therefore, researchers have delicately constructed nanocomposite structural materials by combining noble metal nanomaterials and MOFs in various forms in recent years. Due to the synergistic effect of the two, a series of novel characteristics have been generated, enriching the application fields of MOFs materials and significantly improving their performance. In this paper, the application progress of Au, Ag, Pt and other noble metal /MOFs nanocomposite structural materials in catalysis, sensing, biomedicine and hydrogen storage in recent years is reviewed, which provides new ideas for preparing new nanocomposite materials and exploring new applications.
- metal-organic framework /
- noble metal /
- nanocomposite structure /
- catalyst /
- sensing /
- cancer treatment

HTML全文

图 1 MOFs与贵金属纳米材料催化应用示意图：(a) 光催化HER过程中Au@NH2-UiO-66/CdS的光诱导载流子动力学示意图^[39]； (b) Pt(2)/NH2-UiO-68、Pt(1)@NH2-UiO-68、Pt(2)@NH2-UiO-68和Pt(4)-NH2UiO-68混合光催化剂的合成过程示意图^[43]；(c) Pt和NH2-UiO-68界面电子转移过程示意图^[43]；(d) 催化剂NPs@ZIF-8的组装和CO₂光催化转化示意图^[44]；(e) ALD反应周期的四个脉冲^[46]；(f) MOF涂层包覆在银纳米线及杂化催化剂对MB降解机制示意图^[47]；(g) Ag@MOF-525复合催化剂的合成路线^[48]；(h) 降解过程示意图^[48]；(i) Ru@Mo-MOF-tri的机制示意图^[50]；(j) Pd/ Ti-MOF的合成及NB还原N-甲酰化反应装置示意图^[52]；(k) 光催化NB在Pd1.5%/Ti-MOF上N-甲酰化的机制^[52]；(l) HT Au@MOF复合材料电催化NRR的图解^[54]

Figure 1. Schematic illustration of catalytic applications of MOFs and noble metal nanomaterials: (a) Schematic illustration of the photo-induced carrier dynamics of Au@NH₂-UiO-66/CdS in the photocatalytic HER process^[39]; (b) Schematic diagram of the synthetic process of Pt(2)/NH₂-UiO-68, Pt(1)@NH₂-UiO-68, Pt(2)@NH₂-UiO-68, and Pt(4)-NH₂UiO-68 hybrid photocatalysts^[43]; (c) Schematic illustration of electron transfer process at the Pt and NH₂-UiO-68 interface^[43]; (d) Schematic illustration of the assembly of the catalysts NPs@ZIF-8 and CO₂ photocatalytic conversion^[44]; (e) The four pulses of an ALD reaction cycle^[46]; (f) Schematic diagram of MB degradation mechanism of a hybrid catalyst coated with MOF on silver nanowires^[47]; (g) Degradation efficiency under MOF and MOF/Pt-2 in 5 reaction cycles^[48]; (h) Diagram of the degradation process^[48]; (i) The mechanism diagram of Ru@Mo-MOF-tri^[50]; (j) Schematic Illustration of the Synthesis of the Pd/ Ti-MOF and the Reaction Setup Used for the Reductive NFormylation of NB^[52]; (k) Mechanism of Photocatalytic N-Formylation of NB over the Pd1.5 %/Ti-MOF^[52]; (l) Illustration of the electrocatalytic NRR by HT Au@MOF composite^[54]

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图 2 MOFs与贵金属纳米材料生物医学应用示意图：(a) Ag/Co-TCPP NS光动力协同Ag⁺释放抗菌性能示意图^[90]；(b) Ag@MOF@PDA的合成路线及其协同抗菌和抗生物膜作用示意图^[91]；(c) 基于图Pt-MOF@Au@QDs/PDA的合成路线及氢光热治疗机制示意图^[92]；(d) Pd@ MOF-525@HA的制备和增强光动力和声动力治疗的过程^[93]；(e) ICG-PtMGs@HGd纳米平台作为H₂O₂驱动的氧合器，用于FL/MOST/CT/MRI多模式成像引导的实体瘤PDT和PTT协同治疗的示意图^[94]；(f) 以dYNH靶向肽(BCAMMD)修饰BYL719-顺铂负载双壳纳米粒子(BYL719&Cisplatin@Au@MOF@MS-ICG, BCAMM)的合成工艺方案及BCAMMD在肿瘤细胞中的抗肿瘤机制^[95]

Figure 2. Schematic diagram of MOFs related to biomedical applications of noble metal nanomaterials: (a) Schematic diagram of the photodynamic synergistic Ag⁺ release antibacterial performance of Ag/Co-TCPP NSs^[90]; (b) Schematic illustration of the synthetic route of the Ag@MOF@PDA and its synergistic antibacterial and anti-biofilm effect^[91]; (c) Schematic illustration of the synthesis route and the hydrogen-photothermal treatment therapeutic mechanism based on the Pt-MOF@Au@QDs/PDA^[92]; (d) Scheme illustration showing the preparation of Pd@ MOF-525@HA and enhancement of photodynamic and sonodynamic therapy^[93]; (e) Schematic illustration of the ICG-PtMGs@HGd nanoplatforms as H₂O₂-driven oxygenator for FL/MOST/CT/MRI multimodal imaging guided enhanced PDT and PTT synergistic therapy in a solid tumor^[94]; (f) The scheme of synthetic procedure for BYL719-cisplatin loaded double shell nanoparticle (BYL719&Cisplatin@Au@MOF@MS-ICG, BCAMM) modified with dYNH targeting peptide (BCAMMD) and antitumor mechanisms of BCAMMD in tumor cell^[95]

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表 1 Au纳米颗粒与MOFs复合材料在传感器中应用

Table 1. Applications of Au nanoparticles and MOFs composites in sensors

Material	Target analysis	Method	Linear range	Limit of detection (LOD)	Ref.
Au-MOF-5	Nitrite Nitrobenzene	CV CV	5.0 µmol·L⁻¹ ~ 65.0 mmol·L⁻¹ 20 ~ 500 µmol·L⁻¹	1.0 µmol·L⁻¹; 15.3 µmol·L⁻¹	[58]
Au/SWNTs@MOF-199	Pb²⁺	CV, DPV	1 pmol·L⁻¹ ~ 10 mmol·L⁻¹	25 pmol·L⁻¹	[59]
MIP-Au@MOF-235@g-C₃N₄	Fenamiphos	CV, EIS, DPV	0.01 ~ 16.4 μmol·L⁻¹	0.00713 µmol·L⁻¹	[60]
Au NPs/CoFe LDO/MoS₂ NFs	Alpha-fetoprotein	CV	10⁻⁵ ~ 100 ng·mL⁻¹	3.23 fg·mL⁻¹	[61]
Apt-Au@PEIM/AFM₁/MIP-Apt/ Au NPs/GCE	Aflatoxin M₁	CV, EIS, DPV	0.01 ~ 200 nmol·L⁻¹	0.07 nmol·L⁻¹	[62]
Au/Ti-MOF/SPE	Gallic acid	CV, DPV	0.01 ~ 100 µmol·L⁻¹	0.05 µmol·L⁻¹	[63]
Au/Cu-MOF/SWNH	Neutrophil gelatinase- associated lipocalin	SWV, i−t	0.00001 ~ 10 ng·mL⁻¹	0.0074, 0.0405 pg·m L⁻¹	[64]
Au_nano/Fe-MOF/GCE	As(Ⅲ)	EIS, SWASV	—	0.0085 ng·L⁻¹	[65]
Cu₂O@Cu-MOF@Au-HRP-Ab₂	Carcinoembryonic antigen	CV, EIS	50 fg·mL⁻¹ ~ 80 ng·mL⁻¹	17 fg·mL⁻¹	[66]
Au NPs/Zn MOF	miRNA-522	CV, EIS	10⁻¹⁵~ 10⁻¹⁰ mol·L⁻¹	3×10⁻¹⁶ mol·L⁻¹	[67]
Au NPs/MOF-5	DNA	CV	1 ~ 100 nmol·L⁻¹	0.05 pmol·L⁻¹	[68]
Au NPs/MOF-199	5-Hydroxyindole-3-acetic acid	SERS	10⁻⁹ ~ 10⁻⁵ mol·L⁻¹	6.40×10⁻¹¹ mol L⁻¹	[82]
Au/MOF-74	4-Nitrothiophenol	SERS	0.10~10 μmol·L⁻¹	69 nmol·L⁻¹	[83]
Au NPs/Cu-TCPP MOFNs	Acrylamide	SERS	0.1 nmol·L⁻¹~10 μmol·L⁻¹	0.08 nmol·L⁻¹	[84]
Si/Au@Ag/ZIF-67	4-Aminothiophenol	SERS	10⁻⁷ ~ 10⁻⁵ mol·L⁻¹	2.0 × 10⁻⁹ mol·L⁻¹	[85]
Ni-MOF-Au@Ag NPs	Thiram, Diquat, Paraquat	SERS	0.01 ~ 50 mg·L⁻¹	87.1, 188.8, 8.9 μg·L⁻¹	[86]
Notes: SWV— Square wave voltammetry ; i-t —Current time curve ; SWASV —Square wave anodic stripping voltammetry; MIP—Molecularly imprinted polymers ; GCE —Glassy carbon electrode ; SWNH—Singlewalled carbon nanohorns; PEIM—PEI(Polyethyleneimine)-MIL-101(Cr); Apt—Aptamer; AFM1—Aflatoxin M1; SPE —Screenprinted electrode; Au_nano—Gold nanoparticles; HRP—Horseradish peroxidase; Ab₂—Secondary antibody; SERS—surface enhancement of Raman scattering; CV—Cyclic voltammetry; EIS—Electrochemical impedance spectroscopy; DPV—Differential pulse voltammetry.

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