Active Site Tailoring of Ni‐Based Coordination Polymers for High‐Efficiency Dual‐Functional HER and UOR Catalysis

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(3)

Published: Oct. 11, 2023

Abstract Ni‐based electrocatalysts are regarded as highly promising ones for urea‐assisted electrolytic water hydrogen production technology. However, during the urea oxidation reaction (UOR) process, their activity is significantly constrained by unavoidable Ni species self‐oxidation reaction, and harmful liquid‐phase products (NO x − ) generated from over‐oxidize also often neglected. Herein, A self‐supported W‐doped Ni‐C 3 S N ‐based coordination polymer electrode (W‐NT@NF) with tailored 3+ active sites using ligand anchoring high‐valence metal doping strategies synthesized, which certified that this pyrolysis‐free catalyst achieves dual‐functional evolution (HER) UOR performance comparable to reported noble metal/non‐noble catalysts, both achieving high current densities approaching 1000 mA cm −2 . Density functional theory (DFT) calculations, combined spectroscopic characterizations record dynamic of oxygen (OER) processes, reveal novel energetically favorable pathway proposed, initiates directly without involve participation reconstructed NiOOH resulting OER. combination in‐line gas chromatography, ion chromatography analysis indicates Faradaic efficiency (FE) 2 higher (34%) at lower (<100 ), FE NO remains below 20% in long‐term electrolysis.

Language: Английский

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Layered metal-organic frameworks and metal-organic nanosheets as functional materials

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 472, P. 214787 - 214787

Published: Aug. 29, 2022

Language: Английский

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Influence of the Solvent on the Assembly of Ni3(hexaiminotriphenylene)2 Metal–Organic Framework Nanosheets at the Air/Liquid Interface

Bulletin of the Chemical Society of Japan, Journal Year: 2023, Volume and Issue: 96(3), P. 274 - 282

Published: March 1, 2023

Abstract Nanosheets of metal–organic frameworks (MOFs)—porous crystalline materials consisting metal ions and organic ligands—are actively studied for their intrinsic chemical/physical properties attributed to the reduced dimensionality potential function as ideal components nanodevices, especially when electrical conduction is present. Air/liquid interfacial synthesis a promising technique obtain highly oriented MOF nanosheets. However, rational control size shape combined with aimed functionality remains an important issue address making it necessary research critical factors governing nanosheet characteristics in synthesis. Here, we investigate influence solvent—methanol (MeOH) versus N,N-dimethylformamide (DMF)—used prepare ligand spread solution on assembly nanosheets composed Ni2+ 2,3,6,7,10,11-hexaiminotriphenylene (HITP) (HITP-Ni-NS). We find that macroscopic morphological uniformity micrometer scale higher DMF used solvent. Regarding microscopic domain, molecules relatively high polarity boiling point are involved HITP-Ni-NS formation, hindering its growth resulting slightly smaller lateral than grown MeOH used. These findings provide crucial guidelines towards establishing judicious strategy creating desired at air/liquid interface, thereby driving forward both fundamental applied aspects this field.

Language: Английский

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Rapid, external acid-free synthesis of Bi2WO6 nanocomposite for efficient supercapacitor application

Journal of the Taiwan Institute of Chemical Engineers, Journal Year: 2023, Volume and Issue: 143, P. 104697 - 104697

Published: Jan. 28, 2023

Language: Английский

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Construction of Heterometallic Coordination Nanosheets Comprising Both Inert and Labile Metal Ions Together via Metalloligand Approach

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Construction of coordination nanosheets (CONASHs) containing both inert and labile metal ions together is fundamentally significant but remains synthetically unachievable until now difficult to realize via conventional synthetic approach CONASHs due variable complexation conditions between heterometal organic ligands. Here, we demonstrate a strategy harness into structure by introducing the concept metalloligand. Metalloligands comprising ion (Os2+/Ru2+) free coordinating sites are designed synthesized can be further used as ligand bind (Fe2+) for building heterometallic (HMCONASHs). Following this, two HMCONASHs homoleptic complexes constructed that show broad absorption electrochemical window with reversible dual redox activity. Further, HMCONASH films exhibit multicolor electrochromism at different voltages, indicating their potential various applications. This may open create diverse structures functions hard achieve traditional approach.

Language: Английский

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Identifying And Unveiling the Role of Multivalent Metal States for Bidirectional UOR and HER Over Ni, Mo‐Trithiocyanuric Based Coordination Polymer

Small, Journal Year: 2023, Volume and Issue: 19(44)

Published: July 7, 2023

Urea oxidation reaction (UOR), an ideal alternative to oxygen evolution (OER), has received increasing attention for realizing energy-saving H2 production and relieving pollutant degradation. Normally, most studied Ni-based UOR catalysts pre-oxidate NiOOH then act as active sites. However, the unpredictable transformation of catalyst's structure its dissolution leaching, may complicate accuracy mechanism studies limit further applications. Herein, a novel self-supported bimetallic Mo-Ni-C3 N3 S3 coordination polymers (Mo-NT@NF) with strong metal-ligand interactions different O/urea adsorption energy are prepared, which realize bidirectional UOR/hydrogen (HER) pathway. A series Mo-NT@NF is prepared through one-step mild solvothermal method their multivalent metal states HER/UOR performance relationship evaluated. Combining catalytic kinetics, in situ electrochemical spectroscopic characterization, density-functional theory (DFT) calculations, pathway proposed by N, S-anchored Mo5+ reconstruction-free Ni3+ sites center HER UOR, respectively. The effective anchoring fast transfer intermediate H* N S ligand C3 H3 contribute kinetic catalysis. Ultimately, coupled HER||UOR system electrodes can achieve energy-efficient overall-urea electrolysis production.

Language: Английский

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Ferric Oxide Nanocrystals‐Embedded Co/Fe‐MOF with Self‐Tuned d‐Band Centers for Boosting Urea‐Assisted Overall Water Splitting

Small, Journal Year: 2023, Volume and Issue: 20(11)

Published: Nov. 7, 2023

Abstract A novel semiconductive Co/Fe‐MOF embedded with Fe 2 O 3 nanocrystals (Fe @CoFe‐MOF) is developed as a trifunctional electrocatalyst for the urea oxidation reaction (UOR), oxygen evolution (OER), and hydrogen enhancing efficiency of production via urea‐assisted overall water splitting. @CoFe‐TPyP‐MOF comprises unsaturated metal‐nitrogen coordination sites, affording enriched defects, self‐tuned d ‐band centers, efficient π – interaction between different layers. Density functional theory calculation confirms that adsorption can be optimized at @CoFe‐TPyP‐MOF, realizing intermediates desorption final product CO N characterized by in situ Fourier transform infrared spectroscopy. The two‐electrode splitting device‐assembled illustrates low cell voltage 1.41 V versus reversible electrode current density 10 mA cm −2 , attaining rate 13.13 µmol min −1 1 m KOH 0.33 urea. electrochemical Raman spectra other basic characterizations used uncover undergoes structural reconstruction after UOR test, while it demonstrates irreversible OER measurement. This work redounds progress spitting production.

Language: Английский

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Fine Pore‐Structure Engineering by Ligand Conformational Control of Naphthalene Diimide‐Based Semiconducting Porous Coordination Polymers for Efficient Chemiresistive Gas Sensing

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(2)

Published: Nov. 15, 2022

Abstract Exploring new porous coordination polymers (PCPs) that have tunable structure and conductivity is attractive but remains challenging. Herein, fine pore engineering by ligand conformation control of naphthalene diimide (NDI)‐based semiconducting PCPs with π stacking‐dependent tunability achieved. The stacking distances in these isoreticular were modulated employing metal centers different geometries. As a result, three conjugated (Co−pyNDI, Ni−pyNDI, Zn−pyNDI) varying obtained. Their crystal structures determined three‐dimensional electron diffraction. through‐space charge transfer result selectivity sensitivity gas sensing. Zn−pyNDI can serve as room‐temperature operable chemiresistive sensor selective to acetone.

Language: Английский

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Enhanced Redox Storage and Diverse Intercalation in Layered Metal Organic Frameworks with a Staggered Stacking Mode

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(4), P. 1572 - 1580

Published: March 18, 2024

Two-dimensional metal organic frameworks (2D MOFs) with honeycomb-like porous sheets are of growing interest for applications in electrochemical energy storage and electrocatalysis. Notably, 2D MOFs that host their eclipsed or slipped-parallel stacking modes possess continuous one-dimensional pores (1D) have been widely studied. In contrast, related a staggered mode reduced porosity, relatively rare, largely unexplored applications. Here we report 2-fold enhanced redox intercalation diverse ions staggered-stacked, nonporous MOF over its eclipsed-stacked, counterpart. Interestingly, both MOFs, despite undergoing similar ligand-centered processes, differ by storing four two electrons per formula unit the phases, respectively. Taken together, mode-dependent modulation ligand's behavior offers new avenue to tune structure–property relationships presents important motivation explore MOFs.

Language: Английский

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Macromolecules incorporating transition metals in the treatment and detection of cancer and infectious diseases: Progress over the last decade

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 510, P. 215732 - 215732

Published: March 28, 2024

Language: Английский

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