Integrating Semiconductor Quantum Dots with Metal–Organic Frameworks: ZnS@Dy-MOF as Robust Bifunctional Catalyst for Overall Water Splitting

Muhammad Sajjad; Zohaib Ashraf; Waseem Shoukat; Muhammad Sajid; Rahman Shah Zaib Saleem; Muhammad Fahad Saeed; Muhammad Naeem Ashiq; Francis Verpoort; Adeel Hussain Chughtai

doi:10.1007/s12209-026-00477-1

Transactions of Tianjin University ›› :1 -16. DOI: 10.1007/s12209-026-00477-1

Research Article

research-article

Integrating Semiconductor Quantum Dots with Metal–Organic Frameworks: ZnS@Dy-MOF as Robust Bifunctional Catalyst for Overall Water Splitting

Author information +

¹Institute of Chemical Sciences, Bahauddin Zakariya University, 60800, Multan, Pakistan

²Department of Chemistry and Chemical Engineering, Syed Babar Ali School of Science and Engineering, Lahore University of Management Sciences, 54792, Lahore, Pakistan

³School of Chemistry and Chemical Engineering, Shandong University of Technology, 255049, Zibo, China

⁴State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 430070, Wuhan, China

⁵Joint Institute of Chemical Research (FFMiEN), Peoples Friendship University of Russia, RUDN University, Moscow, Russia

^a francis@whut.edu.cn

^b adeelhussain@bzu.edu.pk

Francis Verpoort

Francis Verpoort is Professor at Wuhan University of Technology, where he also serves as the Director of the Functional Hybrid Materials Laboratory (FHML). His research focuses on the structural and mechanistic understanding of organometallic materials, particularly Metal–Organic Frameworks (MOFs) and Porous Organic Polymers (POPs), for applications in electro-, photo-, and thermo-catalysis. He aims to translate fundamental insights into the development of advanced functional technologies. Prof. Verpoort has received numerous distinctions, including the prestigious Dr. Basudev Banerjee Memorial Award (India), Fellowship of the Indian Chemical Society (ICS), and Fellowship of the Royal Society of Chemistry (RSC). In recognition of his scholarly excellence, he has also been elected a member of several eminent academic societies, including the European Academy of Sciences and Arts, the Russian Academy of Natural Sciences, the Mexican Academy of Sciences, and the World Academy of Sustainable Development. He is Chair of the “Palladium Global Science Award” and is included in the Elsevier China Highly Cited Researcher list, and for the fifth consecutive year in the TOP 2% Scientist List of Stanford University.

Adeel Hussain Chughtai

Adeel Hussain Chughtai received his M.Sc. degree in 2002 and M.Phil in 2007 from the Institute of Chemical Sciences, Bahauddin Zakariya University (BZU), Multan, Pakistan. He joined the Faculty of Science at BZU as a Lecturer in 2008. Later, he obtained his doctoral degree in 2016 from State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, China, under the supervision of Prof. Dr. Francis Verpoort (FICS, FRSC, DF-IETI) with support from the China Scholarship Council (CSC No: 2013CXZ988). During his doctoral studies, Dr. Chughtai was awarded the Certificate of Excellent Academic Student for the academic year 2014–2015 and the Outstanding International Graduate Student Award in 2016 by Wuhan University of Technology. Currently, he is serving as an Associate Professor at Institute of Chemical Sciences, Bahauddin Zakariya University. He received the Research Productivity Award (RPA) from the Pakistan Council of Science and Technology (PCST) in both 2016 and 2017. His research focuses on: Synthesis of thiosemicarbazones, thiazoles, and thiazolidinones, Biological screening and Molecular Docking studies, Design and synthesis of metal–organic frameworks (MOFs), Applications of MOFs in catalysis, photocatalysis, sensing, and drug delivery.

Show less

History +

PDF

Abstract

Sluggish kinetics of water electrolysis is a major challenge in the practical dissociation of water to form gaseous H₂ and O₂. Electrocatalysts are required for enhancing the performance of the water splitting process. This study addresses this issue by examining the synthesis of ZnS quantum dots (QDs), a metal–organic framework containing Dy (Dy-MOF), and the composite of these species (ZnS@Dy-MOF), as well as their potential use as electrocatalysts for water splitting. ZnS QDs were integrated into the MOF during synthesis to achieve enhanced conductivity and stability, aiming to harness the synergetic effect in the resulting material. The properties of ZnS@Dy-MOF were exploited in practical use to address the urgent demand for effective water splitting catalysts. The morphological, structural, and compositional properties of the ZnS QDs, Dy-MOF, and ZnS@Dy-MOF were examined via various characterization techniques. The ZnS@Dy-MOF composite emerged as the optimal electrocatalyst for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with a low overpotential of 228 mV for the HER and 138 mV for the OER at a current density of 10 mA/cm². The ZnS@Dy-MOF composite also had a relatively small onset potential of 1.47 V versus RHE with 50 h of electrochemical sustainability. The synergistic interaction between the ZnS QDs and Dy-MOF conferred remarkable catalytic efficiency and significant stability to the electrocatalyst. The foremost objective of this research is to study the extraordinary potential of Dy-MOF and its composites for applications involving water splitting.

Keywords

Zinc sulfide quantum dots / Dysprosium metal–organic framework / Hydrogen evolution reaction / Oxygen evolution reaction / Electrocatalyst

Cite this article

Download citation ▾

Muhammad Sajjad, Zohaib Ashraf, Waseem Shoukat, Muhammad Sajid, Rahman Shah Zaib Saleem, Muhammad Fahad Saeed, Muhammad Naeem Ashiq, Francis Verpoort, Adeel Hussain Chughtai. Integrating Semiconductor Quantum Dots with Metal–Organic Frameworks: ZnS@Dy-MOF as Robust Bifunctional Catalyst for Overall Water Splitting. Transactions of Tianjin University 1-16 DOI:10.1007/s12209-026-00477-1

登录浏览全文

4963

注册一个新账户忘记密码

References

Publishing order | Descend order by publishing year | Descend order by cited within

[1]	Ağbulut Ü, Sarıdemir S. A general view to converting fossil fuels to cleaner energy source by adding nanoparticles. Int J Ambient Energy, 2018, 42: 1569-1574

[2]	Megía PJ, Vizcaíno AJ, Calles JA, et al.. Hydrogen production technologies: from fossil fuels toward renewable sources. A mini review Energy Fuels, 2015, 35: 16403-16415

[3]	Chen Z, Wei W, Ni BJ. Cost-effective catalysts for renewable hydrogen production via electrochemical water splitting: recent advances. Curr Opin Green Sustainable Chem, 2021, 27: 100398

[4]	Amaro-Gahete J, Klee R, Esquivel D, et al.. Fast ultrasound-assisted synthesis of highly crystalline MIL-88A particles and their application as ethylene adsorbents. Ultrason Sonochemistry, 2019, 50: 59-66

[5]	Zhang X, Chen Z, Liu X, Hanna SL, Wang X, Taheri-Ledari R, Maleki A, Li P, Farha OK. A historical overview of the activation and porosity of metal–organic frameworks. Chem Soc Rev, 2020, 49: 7406-7427

[6]	Wu J, Dai Q, Zhang H, Li X. A defect-free MOF composite membrane prepared via in-situ binder-controlled restrained second-growth method for energy storage device. Energy Storage Mater, 2021, 35: 687-694

[7]	Hou Q, Zhou S, Wei Y, et al.. Balancing the grain boundary structure and the framework flexibility through bimetallic Metal-Organic Framework (MOF) membranes for gas separation. J Am Chem Soc, 2020, 142: 9582-9586

[8]	Nandiyanto ABD, Okuyama K. Progress in developing spray-drying methods for the production of controlled morphology particles: from the nanometer to submicrometer size ranges. Adv Powder Technol, 2011, 22: 1-19

[9]	Farha OK, Eryazici I, Jeong NC, et al.. Metal–organic framework materials with ultrahigh surface areas: is the sky the limit?. J Am Chem Soc, 2012, 134: 15016-15021

[10]	Liang C, He J, Zhang Y, et al.. MOF-derived CoNi@C-silver nanowires/cellulose nanofiber composite papers with excellent thermal management capability for outstanding electromagnetic interference shielding. Compos Sci Technol, 2011, 224: 109445

[11]	Furukawa H, Go YB, Ko N, Park YK, Uribe-Romo FJ, Kim J, O’Keeffe M, Yaghi OM. Isoreticular expansion of metal–organic frameworks with triangular and square building units and the lowest calculated density for porous crystals. Inorg Chem, 2011, 50: 9147-9152

[12]	Gao D, Chen JH, Fang S, Ma T, Qiu X-H, Ma J-G, Gu Q, Cheng P. Simultaneous quantitative recognition of all purines including N6-methyladenine via the host-guest interactions on a Mn-MOF. Matter Camb, 2021, 4: 1001-1016

[13]	Bonnett BL, Smith ED, De La Garza M, Cai M, Haag JV, Serrano JM, Cornell HD, Gibbons B, Martin SM, Morris AJ. PCN-222 metal–organic framework nanoparticles with tunable pore size for nanocomposite reverse osmosis membranes. ACS Appl Mater Interfaces, 2020, 12: 15765-15773

[14]	Kim H, Hong CS. MOF-74-type frameworks: tunable pore environment and functionality through metal and ligand modification. CrystEngComm, 2021, 23: 1377-1387

[15]	Deng H, Grunder S, Cordova KE, et al.. Large-pore apertures in a series of metal-organic frameworks. Science, 2012, 336: 1018-1023

[16]	Malik WMA, Afaq S, Mahmood A, et al.. A facile synthesis of CeO₂ from the GO@ Ce-MOF precursor and its efficient performance in the oxygen evolution reaction. Front Chem, 2022, 10: 996560

[17]	Nazar N, Manzoor S, ur Rehman Y, et al.. Metal-organic framework derived CeO₂/C nanorod arrays directly grown on nickel foam as a highly efficient electrocatalyst for OER. Fuel, 2022, 307: 121823

[18]	ur Rehman MY, Manzoor S, Nazar N, et al.. Facile synthesis of novel carbon dots@metal organic framework composite for remarkable and highly sustained oxygen evolution reaction. J Alloys Compd, 2021, 856: 158038

[19]	Ashraf Z, Andleeb M, Sajjad M, et al.. One pot solvothermal synthesis of Zr-MOF and DNA-encapsulated Zr-MOF for improved current density towards OER. Adv Nano Res, 2025, 18: 585-597

[20]	Paul A, Radinović K, Hazra S, et al.. Electrocatalytic behavior of an amide functionalized Mn(II) coordination polymer on ORR, OER and HER. Molecules, 2022, 27: 7323

[21]	Malik WMA, Ismail M, Afaq S, et al.. Synergetic effect of heterostructure graphene oxide and Ce based metal organic framework nanocomposite as electrocatalyst for HER and OER. J Alloys Compd Commun, 2025, 7: 100097

[22]	Fang Y, Ma Y, Zheng M, et al.. Metal–organic frameworks for solar energy conversion by photoredox catalysis. Coord Chem Rev, 2018, 373: 83-115

[23]	Nik Zaiman NFH, Shaari N, Harun NAM. Developing metal-organic framework-based composite for innovative fuel cell application: an overview. Int J Energy Res, 2022, 46: 471-504

[24]	Zhang H, Nai J, Yu L, et al.. Metal-organic-framework-based materials as platforms for renewable energy and environmental applications. Joule, 2017, 1: 77-107

[25]	Wang T, Kou Z, Mu S, et al.. 2D dual-metal zeolitic-imidazolate-framework-(ZIF)-derived bifunctional air electrodes with ultrahigh electrochemical properties for rechargeable zinc–air batteries. Adv Funct Mater, 2018, 28: 1705048

[26]	Sirati MM, Hussain D, Mahmood K, et al.. Single-step hydrothermal synthesis of amine functionalized Ce-MOF for electrochemical water splitting. J Taibah Univ Sci, 2022, 16: 525-534

[27]	Hwang JM, Oh MO, Kim I, et al.. Preparation and characterization of ZnS based nano-crystalline particles for polymer light-emitting diodes. Curr Appl Phys, 2005, 5: 31-34

[28]	Rasheed T, Rizwan K, Bilal M, et al.. Metal-organic framework-based engineered materials—fundamentals and applications. Molecules, 2020, 25: 1598

[29]	Lu G, Zheng H, Lv J, et al.. Review of recent research work on CeO₂-based electrocatalysts in liquid-phase electrolytes. Electrochim Acta, 2020, 480: 229091

[30]	Afaq S, Ashiq F, Shoukat W, et al.. Highly enhanced electro-catalytic behavior of an amide functionalized Cu (II) coordination polymer on OER at large current densities. J Mol Struct, 2025, 1324: 140852

[31]	Yang HL, Bai LF, Geng ZR, et al.. Carbon quantum dots: preparation, optical properties, and biomedical applications. Mater Today Adv, 2023, 18: 100376

[32]	Giri L, Rout SR, R S Varma, et al.. Recent advancements in metal–organic frameworks integrating quantum dots (QDs@MOF) and their potential applications. Nanotechnol Rev, 2022, 11: 1947-1976

[33]	Mohamed WA, Abd El-Gawad H, Mekkey S, et al.. Quantum dots synthetization and future prospect applications. Nanotechnol Rev, 2021, 10: 1926-1940

[34]	Sajjad M, Almufarij R, Ali Z, et al.. Magnetic solid phase extraction of aminoglycosides residue in chicken egg samples using Fe₃O₄-GO-agarose-chitosan composite. Food Chem, 2024, 430: 137092

[35]	Anjum J, Shehzadi SA, Sajid M, et al.. Azadirachta indica assisted green synthesis of magnetic Ag/GO-Fe3O4 nanocomposites for the solid phase extraction of tetracyclines from milk. J Chin Chem Soc, 2024, 71: 1286-1299

[36]	Urrego S, Serra E, Alfredsson V, et al.. Bottle-around-the-ship: A method to encapsulate enzymes in ordered mesoporous materials. Microporous Mesoporous Mater, 2010, 129: 173-178

[37]	Zhan BZ, Li XY. A novel ‘build-bottle-around-ship’ method to encapsulate metalloporphyrins in zeolite-Y. An efficient biomimetic catalyst. Chem Commun, 1998, 3: 349-350

[38]	Lu G, Li S, Guo Z, et al.. Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation. Nat Chem, 2012, 4: 310-316

[39]	Kaur R, Paul A, Deep A. Nanocomposite of europium organic framework and quantum dots for highly sensitive chemosensing of trinitrotoluene. Forensic Sci Int, 2014, 242: 88-93

[40]	Lin X, Gao G, Zheng L, et al.. Encapsulation of strongly fluorescent carbon quantum dots in metal–organic frameworks for enhancing chemical sensing. Anal Chem, 2014, 86: 1223-1228

[41]	Hedau B, Park SJ, Kang BC, et al.. Bifunctional carbon quantum dot-embedded metal-organic framework nanohybrid as a highly efficient electrocatalyst for water splitting and CO₂ reduction. Carbon, 2024, 216: 118527

[42]	Zhou Y, Luo Y, Wan J. A CdS quantum dots-sensitized porphyrin-based MOFs for hydrogen evolution reaction in acid media. J Mater Sci Mater Electron, 2020, 31: 21214-21221

[43]	Sohail M, Ayyob M, Wang A, et al.. Revolutionizing water oxidation: NiSe/NiO heterostructure as a high-performing oxygen evolution reaction catalyst. Int J Hydrog Energy, 2024, 51: 1042-1049

[44]	Jiang HL, Tsumori N, Xu Q. A series of (6,6)-connected porous lanthanide−organic framework enantiomers with high thermostability and exposed metal sites: scalable syntheses, structures, and sorption properties. Inorg Chem, 2010, 49: 10001-10006

[45]	Wei Z, Lu Y, Zhao J, et al.. Synthesis and luminescent modulation of ZnS crystallite by a hydrothermal method. ACS Omega, 2018, 3: 137-143

[46]	Yin Y, Chen H, Lin P, et al.. Flexible fluorescent metal-organic frameworks towards highly stable optical fibers and biocompatible cell platforms. Sci China Mater, 2023, 66: 1659-1669

[47]	Hajiashrafi T, Ahmadi Arjanaki M, Shamsi Z. Lanthanide-based nano-porous coordination polymers (Ln = Tb, Dy, Er) and their application in the glycerol acetalization reaction. Inorg Chem Res, 2024, 8: 67-75

[48]	Saddiqa A, Nisar L, Gilani SR, et al.. Surface-assembled non-noble metal nanoscale Ni-colloidal thin-films as efficient electrocatalysts for water oxidation. RSC Adv, 2019, 9: 37274-37286

[49]	Bao F, Kemppainen E, Dorbandt I, et al.. Understanding the hydrogen evolution reaction kinetics of electrodeposited nickel molybdenum in acidic, near-neutral, and alkaline conditions. ChemElectroChem, 2021, 8: 195-208

[50]	Du J, Wang R, Y R Lv, et al.. One-step MOF-derived Co/Co₉S₈ nanoparticles embedded in nitrogen, sulfur and oxygen ternary-doped porous carbon: an efficient electrocatalyst for overall water splitting. Chem Commun, 2019, 55: 3203-3206

[51]	Wang J, Cui C, Lin R, et al.. Hybrid cobalt-based electrocatalysts with adjustable compositions for electrochemical water splitting derived from Co²⁺-Loaded MIL-53 (Fe) particles. Electrochim Acta, 2018, 286: 397-405

[52]	Yan L, Cao L, Dai P, et al.. Metal-organic frameworks derived nanotube of nickel–cobalt bimetal phosphides as highly efficient electrocatalysts for overall water splitting. Adv Funct Mater, 2017, 27: 1703455

[53]	Zhou J, Dou Y, Wu XQ, et al.. Alkali‐etched Ni (II)‐based metal–organic framework nanosheet arrays for electrocatalytic overall water splitting. Small, 2020, 16: 1906564

[54]	Liang Q, Jin H, Wang Z, et al.. Metal-organic frameworks derived reverse-encapsulation Co-NC@Mo₂C complex for efficient overall water splitting. Nano Energy, 2019, 57: 746-752

[55]	Qian Q, Li Y, Liu Y, et al.. Ambient fast synthesis and active sites deciphering of hierarchical foam‐like trimetal–organic framework nanostructures as a platform for highly efficient oxygen evolution electrocatalysis. Adv Mater, 2019, 31: 1901139

[56]	Zhou W, Xue Z, Liu Q, et al.. Trimetallic MOF‐74 films grown on Ni foam as bifunctional electrocatalysts for overall water splitting. Chemsuschem, 2020, 13: 5647-5653

[57]	Van Phuc T, Jana J, Ravi N, et al.. Highly active Ni/Co-metal organic framework bifunctional electrocatalyst for water splitting reaction. Int J Hydrog Energy, 2022, 47: 22787-22795