Ring-Shaped Polyoxometalate Built by {Mn ₄ PW ₉ } and PO ₄ Units for Efficient Visible-Light-Driven Hydrogen Evolution

Open AccessCCS ChemistryCOMMUNICATION1 Aug 2021Ring-Shaped Polyoxometalate Built by {Mn4PW9} and PO4 Units for Efficient Visible-Light-Driven Hydrogen Evolution Hai-Lou Li, Mo Zhang, Chen Lian, Zhong-Ling Lang, Hongjin Lv Guo-Yu Yang Li MOE Key Laboratory of Cluster Science, School Chemistry Chemical Engineering, Beijing Institute Technology, 102488 Google Scholar More articles this author , Zhang Lian Lang *Corresponding authors: E-mail Address: [email protected] College Chemistry, Northeast Normal University, Changchun, Jilin 130024 https://doi.org/10.31635/ccschem.020.202000403 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesTrack Citations ShareFacebookTwitterLinked InEmail A novel mixed-valence, ring-shaped multinuclear Mn-containing polyoxometalate, [H2N(CH3)2]15NaH8-[MnIII3MnIV(?3-O)3(OAc)PO4(B-?-PW9O34)]4·36H2O ( 1) was made systematically characterized using various spectroscopic computational techniques. Its polyoxoanion can be described as a tetramer four [MnIII3MnIV(?3-O)3(OAc)(B-?-PW9O34)]3? ({MnIII3MnIV(PW9)}) clusters linkers. Significantly, structurally new complex 1 efficiently catalyze hydrogen evolution with 23 ?mol H2 gas after 12 h visible-light irradiation three-component system. We propose possible catalytic hydrogen-evolving mechanism based on both experimental results density functional theory (DFT) calculations. Download figure PowerPoint Introduction Polyoxometalates (POMs) have attracted considerable research interest due their structural diversity potential applications in medicine, catalysis, materials science, photochemistry, molecular magnetism, so forth.1–7 The versatile lacunary POM fragments generated removing one or more skeletal MO6 groups serve multidentate O-donor inorganic ligands construct mono- transition-metal-substituted polyoxometalates (TMSPs).8–15 Currently, the design preparation high-nuclearity TMSPs remain most interesting topics synthetic chemistry. To date, been such [H56Fe28P8W48O248]28?,16 [{Co4(OH)3PO4}4(PW9O34)4]28?,17 [Cu20Cl(OH)2(H2O)12(P8W48O184)]25?,18 [H6Ni20P4W34(OH)4O136(enMe)8(H2O)6]6?,19 [{Ni6(Tris)(en)3(BTC)1.5(PW9O34)}8]36?,1 [Zr24O22(OH)10(H2O)2(W2O10H)2(GeW9O34)4(GeW8O31)2]32?.11 Among categories TMSPs, assembly POMs (Mn-POMs) has continuously developed into intriguing subjects considering extraordinary performance field magnetism recently photocatalysis.8,20 Until now, number Mn-POMs different vacant are well documented; however, there far fewer examples bearing than 10 manganese atoms. Representative these structurally, magnetically, catalytically include [MnIV2MnIII6MnII4(?3-O)6(?-OH)4(H2O)2(CO3)6(SiW6O26)2]18?,21 [MnIII13MnIIO12(PO4)4(PW9O34)4]31?,22 [{MnIII3MnIV4O4(OH)2(OH2)}2(W6O22)(H2W8O32)2(H4W13O46)2]26?,23 [MnIII10MnII6O6(OH)6(PO4)4(SiW9O34)4]28?, [MnIII4MnII12(OH)12PO4)4(SiW9O34)4]28?,24 [MnII19(OH)12(SiW10O37)6]28?,25 [MnIII20(OH)8(H2O)8(O3P(CH2)6PO3)6(A-PW9O34)8]44?,26 [(P8W48O184){(P2WIII14Mn4O60)(P2W15MnIII3O58)2}4]144?,27 [{MnIV24MnIII12O28(H2O)23}2(W24O120)2]40?28 Supporting Information Table S1). Therefore, construction remains an explore. In addition syntheses Mn-POMs, studies properties attract tremendous attention, especially renewable energy exploration.29 containing {Mn4O4} cubane moieties investigated excellent candidates photocatalysis, they potentially essential role exploration clean sources. Literature reports show that moiety may work model oxygen-evolving center, {Mn4O5Ca}, natural photosystem II; its atomic structure solved advanced crystallographic technique.29–32 However, case used catalyzing water oxidation reactions under chemical photochemical conditions,33–36 but little reported proton reduction generate fuel.37,38 Herein, we report tetramer, [H2N(CH3)2]15NaH8[MnIII3MnIV(?3-O)3(OAc)(PO4)(B-?-PW9O34)]4·36H2O 1), {B-?-PW9O34}-stabilized connected linkers explore property visible-light-driven production. Results Discussion Black strip crystal hydrothermally combining Na9[A-PW9O34]·7H2O, Na2CO3, MnCl2·4H2O, [H2N(CH3)2]Cl, KMnO4 molar ratio 1.00?3.97?17.25?20.88?2.71. worked source high-valence MnIV leading formation (experimental details Information; Figures S1–S4). Parallel experiments revealed presence [H2N(CH3)2]Cl during process is vitally important producing target cluster 1. absence replacement other ammonium salts (e.g., N(CH3)4Br, N(C4H9)4Br, etc.) does not yield final product. Single-crystal X-ray diffraction shows crystallizes monoclinic space group C2/c S2). contains unique tetrameric [MnIII3MnIV(?3-O)3(OAc)(PO4)(B-?-PW9O34)]424? 1a), Na+, 15[H2N(CH3)2]+, 36H2O. Bond valence sum (BVS) calculations reveal all W P atoms 1a +6 +5 states S3), respectively.39 BVS values Mn1–Mn8 3.801, 3.222, 3.142, 3.211, 3.146, 3.249, 3.779, 3.179, respectively, suggesting Mn2–Mn6 Mn8 +3 states, whereas Mn1 Mn7 +4 states. Moreover, Mn centers were also photoelectron spectroscopy (XPS), which integrated areas MnIII approximately 1?3 Figure S4). XPS consistent calculations, each centers.40 (Figure 1b) ring shape {MnIII3MnIV(PW9)} subunits 1a). Such connection acting pure ?2-bridging units rare distinctive from previous where participation usually stabilize high nuclear cores structure.41–47 Particularly, tetrahedral [B-?-PW9O34]9? ({PW9}) 2d) situ isomerization [A-?-PW9O34]9? precursor 2c) hydrothermal reaction. Each subunit composed typical [MnIII3MnIV(?3-O)3(OAc)]6+ ({Mn4}) 2a) anchored trivacant Keggin {PW9} unit via six ?-O ?4-O 1; S5a S5b). | (a) Combined polyhedral ball-and-stick representation {MnIII3MnIV(?3-O3)(OAc)(B-?-PW9O34)} groups. (b) 1a. Color codes atoms: WO6, red; PO4, purple; MnIIIO6, yellow; MnIVO6, orange; C, black. 2 {MnIII3MnIV(?3-O3)(OAc)} cluster. {MnIII3MnIV(?3-O3)(OAc)(PO4)}4 (c) [A-?-PW9O34]9– precursor. (d) [B-?-PW9O34]9– (e) A: –x, y, 0.5–z. P/PO4, MnIII, MnIV, O, {Mn4} cubane, exhibit six-coordinated octahedral geometry [MnIII?O: 1.883(11)?2.287(10) Å MnIV?O: 1.896(9)?2.012(8) Å]; occupy vertexes simplified tetrahedron MnIII?MnIII MnIII?MnIV distances 3.180?3.255 2.828?2.969 Å, respectively S5c). acts exclusively ?2-linker bridging two adjacent 2b). best our knowledge, represents first example linker chemistry.48 Alternatively, perceived [MnIII12MnIV4(?3-O)12 (OAc)4P4O16]12+ ({Mn16P4}) surrounded evenly-distributed 24 ?2-O 4 2e). {Mn16P4} ring, connects cubanes O 1b, 2b, 2e; S6a S6b), node additionally stabilized OAc– apart coordinating units. Interestingly, 16-membered (dimensions: 7.8 × Å2) formed (Mn1, Mn7, Mn1A, Mn7A), P, 8 S6c). Additionally, packing viewed along b-axis S7a) three-dimensional S7b), arranged –AAA– mode a-, b-, c-axis. activity examined well-established system; amount produced quantified chromatography TCD (Thermal Conductivity Detector).49 Photolysis deaerated solution catalyst (20 ?mol/L), [Ir(ppy)2(dtbbpy)]+ (0.2 mmol/L), triethanolamine (TEOA) (0.25 mol/L), H2O (2 mol/L) 6 mL CH3CN/DMF (1?3 v/v) blue light-emitting diode (LED) (? = 450 nm, 45 mW/cm2) at 15 degC; 3a); concomitant observed indicated color change yellow green S8 S9). No detected addition, cyclic voltammograms TBA+ salt showed quasireversible redox waves range –1.5 1.5 V versus SCE. positive domain MnIV/III MnIII/II peaks 1.14 0.78 SCE, respectively. When further negative domain, CV W-based reductions S10a). Addition trifluoroacetic acid leads substantial current enhancement, indicating reduced S10b). Upon exposure nm visible light, increases linearly time, while no dark. After irradiation, obtained, corresponding turnover (TON) ?192, highest value, among known catalyzed H2-evolving systems.37,38 encourages us photolysis conditions. Control any component (catalyst 1, TEOA, [Ir(ppy)2(dtbbpy)]+, H2O) yields negligible 3a). Additional control fragment 16 equivalents MnCl2 result much lower production (?4 h, respectively). Furthermore, varied concentration TEOA otherwise identical Both increasing (from 0.1 0.4 mmol/L) 0.05 0.25 led increased S11a S11b). Notably, constant when varying 20 ?mol/L, then decreased upon 30 ?mol/L S11c). phenomenon might attributed shielding photons absorbed photosensitizer because absorb light. experiment “mercury poison” test almost effect photocatalytic S12), form nickel nanoparticles process. stability reaction verified comparing IR spectra isolated before photocatalysis S13), good agreement between confirmed did 3 Photocatalytic decay curves (black curve), + 1(50 ?mol/L) (green (blue curve). red fits single exponential decay. (c e) emission function added TEOA. (d f) Stern–Volmer plots quenching [Ir(ppy)2(dtbbpy)]+* TEOA; calculated rate constants 3.1 1011 (mol/L)–1 s–1 1.0 107 s–1, Previous excited state either reductively quenched electron donor oxidatively acceptor.50–52 system, time-resolved luminescence techniques utilized characterize mechanism. Experimental [Ir(ppy)2(dtbbpy)]*+ accelerated (Figures 3b, 3c, 3e). (SV) plot data reveals apparent 3d 3f). Exponential fitting kinetics dye only lifetimes 96, 81, 50 ns, These indicate oxidative reductive exist systems, literature reports.53–55 Based above information, light-induced proposed Scheme S1. Density carried out B3LYP/PCM(H2O)/[6-31G(d,p)/LANL2DZ(Mn&W)] level driving force toward (HER).56–61 Given {MnIII3MnIV(?3-O)3(OAc)(B-?-PW9O34)} basic building block whole compound, herein selected [MnIII3MnIV(?3-O)3(OAc)(PO4)2(B-?-PW9O34)]9– (Mn4O3; S14) working 4a). An S 9/2 ground set calculation consulting reports, allocated ?-spin 3.74, 3.68, 3.85|e| three (Mn2/3/4 labeled S15), center (Mn1) 2.64|e| ?-spin distribution.23 top singly unoccupied MOs mostly core orbitals S16), photo-reduction would preferably occur sites. As Hinnemann et al.,62 HER should able trap protons desorb H2, thus requiring H adsorbed active site ?GH* close zero. electrostatic (MEP; S17) analysis distribution partial charges ?3-O Mn4O3 core, captured it. contrast, release OAc ligand highly exothermic, resulting attack five-coordinated obtain Mn-H intermediate. hypothesized occurs full oxide [MnIII3MnIV(?3-O)3(PO4)2(B-?-PW9O34)]8–; largely limited extremely adsorption energy. identify real 4b), computed ?Eads Mn4O3. ability consistently favorable Mn. Conversely, strong 1e- 2e-Mn4O3 makes desorption challenge. reaches three-electron reduction, approaches zero giving balance adsorption. such, three-electron-reduced represent evolution, voltammetry S8–S10). very likely adsorbing initially subsequently transferring neighboring Mn-H. Computational sites (S1 energies (H-S1) (H-S2) dependent {MnIII3MnIV(?3-O)3(OAc)(PO4)2(B-?-PW9O34)}9–. Conclusion Mn-substituted method. 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