Research Progress in Preparation of Molybdenum⁃Based Quantum Dots

doi:10.12422/j.issn.1006-396X.2023.05.007

Abstract

Abstract:

MoS₂ quantum dots (QDs) have attracted a lot of attention lately due to their excellent fluorescence properties, catalytic activity, and good biocompatibility. There are various ways to prepare MoS₂ QDs since its first preparation in 2010, including hydrothermal, ultrasonic, and etching methods. Even though other molybdenum?based quantum dots like MoP, Mo₂C, Mo₂N, and MoSe₂ have shown great potential in various fields, their preparation methods have rarely been reported. In this article, The preparation methods and research status of these molybdenum?based quantum dots (MoO₂/MoO₃, MoP, Mo₂C, Mo₂N amd MoSe₂) and comparing the advantages and limitations of different preparation methods were discussed. The key problems in the synthesis of these quantum dots and their application prospects in different directions were discussed.

Key words: Quantum dots, Molybdenum based materials, Preparation, Fluorescence, Ultrasonic

摘要：

钼基材料中MoS₂量子点（MoS₂QDs）因其优异的荧光性能、催化活性和良好的生物相容性引起了研究者的广泛关注，自2010年首次制备以来开发了包括水热、超声、刻蚀等多种制备方式。虽然其他钼基量子点如MoP、Mo₂C、Mo₂N、MoSe₂等在电催化、光催化产氢、超级电容器和离子电池等方面极具潜力，但与之相关的制备方法却鲜有报道。对MoO₂/MoO₃、MoP、Mo₂C、Mo₂N、MoSe₂等钼基量子点的制备方法和发展现状进行了总结；讨论了不同制备方法的优点以及局限性，并提出了部分量子点制备所面临的关键问题；对钼基量子点的制备方法和在不同方向的应用前景进行了展望。

关键词: 量子点, 钼基材料, 制备, 荧光, 超声

CLC Number:

TQ136.1

Jiale WANG, Hongda WU, Qiao HAN, Zhanxu YANG. Research Progress in Preparation of Molybdenum⁃Based Quantum Dots[J]. Journal of Petrochemical Universities, 2023, 36(5): 52-59.

王佳乐, 武宏大, 韩乔, 杨占旭. 钼基量子点制备的研究进展[J]. 石油化工高等学校学报, 2023, 36(5): 52-59.

Figures/Tables 3

References 73

1	XU Y， GE R Y， YANG J， et al. Molybdenum disulfide （MoS₂）⁃based electrocatalysts for hydrogen evolution reaction⁃from mechanism to manipulation［J］. Journal of Energy Chemistry， 2022， 74： 45⁃71.
2	GE H， KUWAHARA Y， YAMASHITA H. Development of defective molybdenum oxides for photocatalysis， thermal catalysis， and photothermal catalysis［J］. Chemical Communications， 2022， 58（61）： 8466⁃8479.
3	ABDOLAHI B， GHOLIVAND M B， SHAMSIPUR M， et al. Ordered mesoporous carbon/molybdenum carbide nanocomposite with high electrochemical performance asymmetric supercapacitor［J］. Journal of Alloys and Compounds， 2022， 905： 164185.
4	TIAN L， LI Z， WANG P， et al. Carbon quantum dots for advanced electrocatalysis［J］. Journal of Energy Chemistry， 2021， 55： 279⁃294.
5	余志超，汤振国，张楠，等. CdS量子点修饰TiO₂纳米管及光解水产氢性能研究［J］. 石油化工高等学校学报， 2022， 35（4）： 38⁃45.
	YU Z C， TANG Z G， ZHANG N， et al. TiO₂ nanotubes modified by CdS quantum dots and performance of photocatalytic water splitting for hydrogen［J］. Journal of Petrochemical Universities， 2022， 35（4）： 38⁃45.
6	GAURAV A， JAIN A， TRIPATHI S K. Review on fluorescent carbon/graphene quantum dots： Promising material for energy storage and next⁃generation light⁃emitting diodes［J］. Materials， 2022， 15（22）： 7888.
7	CHI W G， BANERJEE S K. Application of perovskite quantum dots as an absorber in perovskite solar cells［J］. Angewandte Chemie International Edition， 2022， 61（9）： e202112412.
8	PERMATASARI F A， IRHAM M A， BISRI S Z， et al. Carbon⁃based quantum dots for supercapacitors： Recent advances and future challenges［J］. Nanomaterials， 2021， 11（1）： 91.
9	KAUR A， PANDEY K， KAUR R， et al. Nanocomposites of carbon quantum dots and graphene quantum dots： Environmental applications as sensors［J］. Chemosensors， 2022， 10（9）： 367.
10	ZHENG X T， ANANTHANARAYANAN A， LUO K Q， et al. Glowing graphene quantum dots and carbon dots： Properties， syntheses， and biological applications［J］. Small， 2015， 11（14）： 1620⁃1636.
11	HALDAR D， DINDA D， SAHA S K. High selectivity in water soluble MoS₂ quantum dots for sensing nitro explosives［J］. Journal of Materials Chemistry C， 2016， 4（26）： 6321⁃6326.
12	LIN H H， WANG C X， WU J P， et al. Colloidal synthesis of MoS₂ quantum dots： Size⁃dependent tunable photoluminescence and bioimaging［J］. New Journal of Chemistry， 2015， 39（11）： 8492⁃8497.
13	DAI W H， DONG H F， ZHANG X J. A semimetal⁃like molybdenum carbide quantum dots photoacoustic imaging and photothermal agent with high photothermal conversion efficiency［J］. Materials， 2018， 11（9）： 1776.
14	MAO B G， BAO T， YU J， et al. One⁃pot synthesis of MoSe₂ hetero⁃dimensional hybrid self⁃assembled by nanodots and nanosheets for electrocatalytic hydrogen evolution and photothermal therapy［J］. Nano Research， 2017， 10（8）： 2667⁃2682.
15	WANG N， TANG D Y， ZOU H Y， et al. Synthesis of molybdenum oxide quantum dots with better dispersity and bio⁃imaging ability by reduction method［J］. Optical Materials， 2018， 83： 19⁃27.
16	KANG H， LEE T， PARK Y， et al. Colloidal synthetic methods of amorphous molybdenum phosphide nanoparticles for hydrogen evolution reaction catalysts［J］. Korean Journal of Chemical Engineering， 2020， 37（8）： 1419⁃1426.
17	KIM M， PARK Y， LEE T， et al. Transition⁃metal⁃incorporated molybdenum phosphide nanocatalysts synthesized through post⁃synthetic transformation for the hydrogen evolution reaction［J］. International Journal of Energy Research， 2022， 46（12）： 17668⁃17681.
18	MCENANEY J M， CROMPTON J C， CALLEJAS J F， et al. Amorphous molybdenum phosphide nanoparticles for electrocatalytic hydrogen evolution［J］. Chemistry of Materials， 2014， 26（16）： 4826⁃4831.
19	NKABINDE S S， NDALA Z B， SHUMBULA N P， et al. Delineating the role of crystallinity in the electrocatalytic activity of colloidally synthesized MoP nanocrystals［J］. New Journal of Chemistry， 2020， 44（33）： 14041⁃14049.
20	ALI L， SUBHAN F， AYAZ M， et al. Exfoliation of MoS₂ quantum dots： Recent progress and challenges［J］. Nanomaterials， 2022， 12（19）： 3465.
21	GUO Y M， LI J W. MoS₂ quantum dots： Synthesis， properties and biological applications［J］. Materials Science and Engineering C， 2020， 109： 110511.
22	DHANABALAN S C， DHANABALAN B， PONRAJ J S， et al. 2D⁃materials⁃based quantum dots： Gateway towards next⁃generation optical devices［J］. Advanced Optical Materials， 2017， 5（19）： 1700257.
23	ARUL N S， NITHYA V D. Molybdenum disulfide quantum dots： Synthesis and applications［J］. RSC Advances， 2016， 6（70）： 65670⁃65682.
24	HUANG H， DU C C， SHI H Y， et al. Water⁃soluble monolayer molybdenum disulfide quantum dots with upconversion fluorescence［J］. Particle & Particle Systems Characterization， 2015， 32（1）： 72⁃79.
25	GAO W Y， WANG M Q， RAN C X， et al. Facile one⁃pot synthesis of MoS₂ quantum dots⁃graphene⁃TiO₂composites for highly enhanced photocatalytic properties［J］. Chemical Communications， 2015， 51（9）： 1709⁃1712.
26	WANG X J， WU Q， JIANG K L， et al. One⁃step synthesis of water⁃soluble and highly fluorescent MoS₂ quantum dots for detection of hydrogen peroxide and glucose［J］. Sensors and Actuators B： Chemical， 2017， 252： 183⁃190.
27	MUSCUSO L， CRAVANZOLA S， CESANO F， et al. Optical， vibrational， and structural properties of MoS₂ nanoparticles obtained by exfoliation and fragmentation via ultrasound cavitation in isopropyl alcohol［J］. The Journal of Physical Chemistry C， 2015， 119（7）： 3791⁃3801.
28	WANG T Y， LIU L， ZHU Z W， et al. Enhanced electrocatalytic activity for hydrogen evolution reaction from self⁃assembled monodispersed molybdenum sulfidenanoparticles on an Au electrode［J］. Energy & Environmental Science， 2013， 6（2）： 625⁃633.
29	NGUYEN T P， SOHN W， OH J H， et al. Size⁃dependent properties of two⁃dimensional MoS₂ and WS₂［J］. The Journal of Physical Chemistry C， 2016， 120（18）： 10078⁃10085.
30	LU X L， WANG R G， HAO L F， et al. Oxidative etching of MoS₂/WS₂nanosheets to their QDs by facile UV irradiation［J］. Physical Chemistry Chemical Physics， 2016， 18（45）： 31211⁃31216.
31	DONG L， LIN S， YANG L， et al. Spontaneous exfoliation and tailoring of MoS₂ in mixed solvents［J］. Chemical Communications， 2014， 50（100）： 15936⁃15939.
32	GOPALAKRISHNAN D， DAMIEN D， LI B， et al. Electrochemical synthesis of luminescent MoS₂ quantum dots［J］. Chemical Communications， 2015， 51（29）： 6293⁃6296.
33	LI B L， CHEN L X， ZOU H L， et al. Electrochemically induced Fenton reaction of few⁃layer MoS₂ nanosheets： Preparation of luminescent quantum dots via a transition of nanoporous morphology［J］. Nanoscale， 2014， 6（16）： 9831⁃9838.
34	HAN C C， ZHANG Y， GAO P， et al. High⁃yield production of MoS₂ and WS₂ quantum sheets from their bulk materials［J］. Nano Letters， 2017， 17（12）： 7767⁃7772.
35	LI F， LI J， CAO Z， et al. MoS₂ quantum dot decorated RGO： A designed electrocatalyst with high active site density for the hydrogen evolution reaction［J］. Journal of Materials Chemistry A， 2015， 3（43）： 21772⁃21778.
36	BABY M， KUMAR K R. Synthesis and characterisation of MoS₂ quantum dots by liquid nitrogen quenching［J］. Materials Science and Technology， 2019， 35（12）： 1416⁃1427.
37	WANG Y， LIU Y， ZHANG J F， et al. Cryo⁃mediated exfoliation and fracturing of layered materials into 2D quantum dots［J］. Science Advances， 2017， 3（12）： e1701500.
38	ZHOU K， ZHANG Y， XIA Z N， et al. As⁃prepared MoS₂ quantum dot as a facile fluorescent probe for long⁃term tracing of live cells［J］. Nanotechnology， 2016， 27（27）： 275101.
39	DONG H F， TANG S S， HAO Y S， et al. Fluorescent MoS₂ quantum dots： Ultrasonic preparation， up⁃conversion and down⁃conversion bioimaging， and photodynamic therapy［J］. ACS Applied Materials & Interfaces， 2016， 8（5）： 3107⁃3114.
40	HA H D， HAN D J， CHOI J S， et al. Dual role of blue luminescent MoS₂ quantum dots in fluorescence resonance energy transfer phenomenon［J］. Small， 2014， 10（19）： 3858⁃3862.
41	DAI W H， DONG H F， FUGETSU B， et al. Tunable fabrication of molybdenum disulfide quantum dots for intracellular microRNA detection and multiphoton bioimaging［J］. Small， 2015， 11（33）： 4158⁃4164.
42	CAO H Y， TANG M J， WANG X， et al. Facile and rapid synthesis of emission color⁃tunable molybdenum oxide quantum dots as a versatile probe for fluorescence imaging and environmental monitoring［J］. Analyst， 2020， 145（19）： 6270⁃6276.
43	WANG C D， JIANG J J， RUAN Y J， et al. Construction of MoO₂ quantum dot⁃graphene and MoS₂ nanoparticle⁃graphene nanoarchitectures toward ultrahigh lithium storage capability［J］. ACS Applied Materials & Interfaces， 2017， 9（34）： 28441⁃28450.
44	XU Y， YI R， YUAN B， et al. High capacity MoO₂/graphite oxide composite anode for lithium⁃ion batteries［J］. The Journal of Physical Chemistry Letters， 2012， 3（3）： 309⁃314.
45	LIU X H， YIN Y X， DU F， et al. In situ synthesis of ultrafine metallic MoO₂/carbon nitride nanosheets for efficient photocatalytic hydrogen generation： A prominent cocatalytic effect［J］. Catalysis Science & Technology， 2020， 10（12）： 4053⁃4060.
46	CAO H Y， HU X， SHI W B， et al. pH⁃regulated reversible photoluminescence and localized surface plasmon resonances arising from molybdenum oxide quantum dot［J］. Applied Materials Today， 2020， 18： 100516.
47	XIAO S J， ZHAO X J， HU P P， et al. Highly photoluminescent molybdenum oxide quantum dots： One⁃pot synthesis and application in 2，4，6⁃trinitrotoluene determination［J］. ACS Applied Materials & Interfaces， 2016， 8（12）： 8184⁃8191.
48	XIAO S J， ZHAO X J， ZUO J， et al. Highly photoluminescent MoOx quantum dots： Facile synthesis and application in off⁃on Pi sensing in lake water samples［J］. Analytica Chimica Acta， 2016， 906： 148⁃155.
49	ZHANG Z Y， YANG Z L， CHEN X Y， et al. Facile gradient oxidation synthesizing of highly⁃fluorescent MoO₃ quantum dots for Cr₂O 7 2 - trace sensing［J］. Inorganic Chemistry Communications， 2020， 118： 108001.
50	TONG W Z， AN Y， BAO C X， et al. Improving mechanical properties of copper composite by interconnected MoO₂ quantum dots［J］. Materials Science and Engineering： A， 2022， 848： 143365.
51	QI S P， LIU G N， TAN L， et al. Top⁃down fabrication of colloidal plasmonic MoO_3- x nanocrystals via solution chemistry hydrogenation［J］. Chemical Communications， 2020， 56（35）： 4816⁃4819.
52	LU X L， WANG R G， HAO L F， et al. Preparation of quantum dots from MoO₃ nanosheets by UV irradiation and insight into morphology changes［J］. Journal of Materials Chemistry C， 2016， 4（48）： 11449⁃11456.
53	BORAH D J， MOSTAKO A T T， BORGOGOI A T， et al. Modified top⁃down approach for synthesis of molybdenum oxide quantum dots： Sonication induced chemical etching of thin films［J］. RSC Advances， 2020， 10（6）： 3105⁃3114.
54	BORAH D J， MOSTAKO A T T， MALAKAR A. Tailoring the crystalline phase and size of the MoO₃ quantum dots via sonication induced modified top⁃down method［J］. Journal of Alloys and Compounds， 2022， 891： 161870.
55	YANG F， LIU D Z， LI Y X， et al. Solid⁃state synthesis of ultra⁃small freestanding amorphous MoP quantum dots for highly efficient photocatalytic H₂ production［J］. Chemical Engineering Journal， 2021， 406： 126838.
56	WEI M H， LI B， JIN C， et al. A 3D free⁃standing thin film based on N， P⁃codoped hollow carbon fibers embedded with MoP quantum dots as high efficient oxygen electrode for Li⁃O₂ batteries［J］. Energy Storage Materials， 2019， 17： 226⁃233.
57	ZHANG J L， CHENG Y， CHEN H B， et al. MoP quantum dot⁃modified N，P⁃carbon nanotubes as a multifunctional separator coating for high⁃performance lithium⁃sulfur batteries［J］. ACS Applied Materials & Interfaces， 2022， 14（14）： 16289⁃16299.
58	YU B， MA F， CHEN D J， et al. MoP QDs@graphene as highly efficient electrocatalyst for polysulfide conversion in Li⁃S batteries［J］. Journal of Materials Science & Technology， 2021， 90： 37⁃44.
59	HUANG Y， SONG X N， DENG J， et al. Ultra⁃dispersed molybdenum phosphide and phosphosulfide nanoparticles on hierarchical carbonaceous scaffolds for hydrogen evolution electrocatalysis［J］. Applied Catalysis B： Environmental， 2019， 245： 656⁃661.
60	JIANG E J， LI J Q， LI X L， et al. MoP⁃Mo₂C quantum dot heterostructures uniformly hosted on a heteroatom⁃doped 3D porous carbon sheet network as an efficient bifunctional electrocatalyst for overall water splitting［J］. Chemical Engineering Journal， 2022， 431（Part 4）： 133719.
61	YAN Z H， HUANG Z Y， ZHOU H H， et al. Facile fabrication of MoP nanodots embedded in porous carbon as excellent anode material for potassium⁃ion batteries［J］. Journal of Energy Chemistry， 2021， 54： 571⁃578.
62	CHEN N N， ZHANG W B， ZENG J C， et al. Plasma⁃engineered MoP with nitrogen doping： Electron localization toward efficient alkaline hydrogen evolution［J］. Applied Catalysis B： Environmental， 2020， 268： 118441.
63	FENG W H， YUAN J， GAO F， et al. Piezopotential⁃driven simulated electrocatalytic nanosystem of ultrasmall MoC quantum dots encapsulated in ultrathin N⁃doped graphene vesicles for superhigh H₂ production from pure water［J］. Nano Energy， 2020， 75： 104990.
64	TAN M X， YU C Y， LUAN Q J， et al. The mott⁃schottky heterojunction MoC@NG@ZIS with enhanced kinetic response for promoting photocatalytic hydrogen production［J］. Journal of Materials Chemistry A， 2022， 10（40）： 21465⁃21473.
65	LIU J F， WANG P， FAN J J， et al. Hetero⁃phase MoC⁃Mo₂C nanoparticles for enhanced photocatalytic H₂⁃production activity of TiO₂［J］. Nano Research， 2021， 14（4）： 1095⁃1102.
66	LIU X F， ZHANG X F， DOU Y， et al. Ultrasmall Mo₂C nanocrystals embedded in N⁃doped porous carbons as a surface⁃dominated capacitive anode for lithium⁃ion capacitors［J］. Chemical Communications， 2021， 57（40）： 4966⁃4969.
67	CUI C L， ZHANG G R， YANG Y， et al. Ultra⁃thin carbon bridged MoC quantum dots/g⁃C₃N₄ with charge⁃transfer⁃reaction highways for boosting photocatalytic hydrogen production［J］. Journal of Alloys and Compounds， 2022， 910： 164864.
68	YU B， HUANG A J， CHEN D J， et al. In situ construction of Mo₂C quantum dots⁃decorated CNT networks as a multifunctional electrocatalyst for advanced lithium⁃sulfur batteries［J］. Small， 2021， 17（23）： e2100460.
69	LIN L， SUN Z M， YUAN M W， et al. α⁃MoC_1– x quantum dots encapsulated in nitrogen⁃doped carbon for hydrogen evolution reaction at all pH values［J］. ACS Sustainable Chemistry & Engineering， 2019， 7（10）： 9637⁃9645.
70	LÜ Z， TAHIR M， LANG X W， et al. Well⁃dispersed molybdenum nitrides on a nitrogen⁃doped carbon matrix for highly efficient hydrogen evolution in alkaline media［J］. Journal of Materials Chemistry A， 2017， 5（39）： 20932⁃20937.
71	YUWEN L H， ZHOU J J， ZHANG Y Q， et al. Aqueous phase preparation of ultrasmall MoSe₂ nanodots for efficient photothermal therapy of cancer cells［J］. Nanoscale， 2016， 8（5）： 2720⁃2726.
72	LUAN C Y， XIE S， MA C Y， et al. Elucidation of luminescent mechanisms of size⁃controllable MoSe₂ quantum dots［J］. Applied Physics Letters， 2017， 111（7）： 073105.
73	DHENADHAYALAN N， LIN T W， LEE H L， et al. Multisensing capability of MoSe₂ quantum dots by tuning surface functional groups［J］. ACS Applied Nano Materials， 2018， 1（7）： 3453⁃3463. （编辑喻育红）

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[10]	Zhang Jihong, Zhu Ying. Effect of Oxygen Exposure on the Performance of Polymer Solution  Diluted by the Polymer Flooding Sewage [J]. Journal of Petrochemical Universities, 2015, 28(1): 46-50.
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