An unprecedented {Ni<sub>14</sub>SiW<sub>9</sub>} hybrid polyoxometalate with high photocatalytic hydrogen evolution activity

Paille, Grégoire; Boulmier, Amandine; Bensaïd, Alexandre; Ha‐Thi, Minh‐Huong; Tran, Thu-Trang; Pino, T.; Marrot, Jérôme; Rivière, Éric; Hendon, Christopher H.; Oms, Olivier; Gómez-Mingot, María; Fontecave, Marc; Mellot‐Draznieks, Caroline; Dolbecq, Anne; Mialane, Pierre

doi:10.1039/c9cc01269a

Cited by 55 publications

(40 citation statements)

References 25 publications

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“…Finally, attenuated total reflectance (ATR)‐IR spectra of Co 4 , Co 9 and Co 20 were recorded after the photocatalytic experiments and subsequent precipitation with cesium chloride. These clearly show the characteristic W−O−W bridging and terminal W=O vibrations in the tungsten fingerprint area from 300–1000 cm −1 (Figures S29–S31), which indicates the solution of the polyanions is stable under turnover conditions and represents an established method frequently used for the post‐catalytic study of POMs [23,27] …”

Section: Resultsmentioning

confidence: 94%

Phosphate‐Templated Encapsulation of a {Co^II₄O₄} Cubane in Germanotungstates as Carbon‐Free Homogeneous Water Oxidation Photocatalysts

et al. 2021

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The ever‐growing interest in sustainable energy sources leads to a search for an efficient, stable, and inexpensive homogeneous water oxidation catalyst (WOC). Herein, the PO43− templated synthesis of three abundant‐metal‐based germanotungstate (GT) clusters Na15[Ge4PCo4(H2O)2W24O94] ⋅ 38H2O (Co4), Na2.5K17.5[Ge3PCo9(OH)5(H2O)4W30O115] ⋅ 45H2O (Co9), Na6K16[Ge4P4Co20(OH)14(H2O)18W36O150] ⋅ 61H2O (Co20) with non‐, quasi‐, or full cubane motifs structurally strongly reminiscent of the naturally occurring {Mn4Ca} oxygen evolving complex (OEC) in photosystem II was achieved. Under the conditions tested, all three GT‐scaffolds were active molecular WOCs, with Co9 and Co20 outperforming the well‐known Na10[Co4(H2O)2(PW9O34)2] {Co4P2W18} by a factor of 2 as shown by a direct comparison of their turnover numbers (TONs). With TONs up to 159.9 and a turnover frequency of 0.608 s−1 Co9 currently represents the fastest Co‐GT‐based WOC, and photoluminescence emission spectroscopy provided insights into its photocatalytic WOC mechanism. Cyclic voltammetry, dynamic light scattering, UV/Vis and IR spectroscopy showed recyclability and integrity of the catalysts under the applied conditions. The experimental results were supported by computational studies, which highlighted that the facilitated oxidation of Co9 was due to the higher energy of its highest occupied molecular orbital electrons as compared to Co4.

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Section: Resultsmentioning

confidence: 94%

Phosphate‐Templated Encapsulation of a {Co^II₄O₄} Cubane in Germanotungstates as Carbon‐Free Homogeneous Water Oxidation Photocatalysts

et al. 2021

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“…These POMs can be regarded as multidentate O‐donor ligands due to the affluent oxygen on the surfaces and used to construct various transition metal POM clusters. Combining 3d‐metal ions with POMs not only can help regulate the band gap, but also may broaden the absorption spectrum . Therefore, a number of heterometallic 3d‐POMs have recently been investigated, such as Co, Ni, Cu, Mn and Fe‐based POMs.…”

Section: Heterometallic 3d–4d or 3d–5d (3d‐poms) Clustersmentioning

confidence: 99%

“…Combining 3d-metal ions with POMs not only can help regulate the band gap, but also may broaden the absorption spectrum. [77][78][79][80][81][82] Therefore, a number of heterometallic 3d-POMs have recently been investigated, such as Co, Ni, Cu, Mn and Febased POMs. Thanks to multiple redox active metal sites, such clusters are widely used in photocatalytic water splitting.…”

Section: Heterometallic 3d-4d or 3d-5d (3d-poms) Clustersmentioning

confidence: 99%

Recent Advances in First‐Row Transition Metal Clusters for Photocatalytic Water Splitting

2020

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Water splitting based on first‐row transition metal (3d) photocatalysts is a cost‐effective technology for the conversion of abundant solar energy into useful energy on a large scale. The catalytic core of photosynthetic enzymes is a cubic CaMn4O5 cluster. Illuminated by natural photosynthesis, artificial solar water splitting photocatalysts composed of metal clusters are now being designed and tested. Ideally, such photocatalysts composed of atomically precise metal clusters with regular crystal structures are promising model catalysts that can be used to study structure–performance relationships. Recent advances based on metal cluster designs have improved our understanding of photoinduced charge separation and catalytic water redox reactions. This Minireview summarizes the recent advances in 3d metal cluster photocatalysts with well‐defined structures for photocatalytic water splitting and focuses on different clusters with tunable structures that are capable of achieving better photocatalytic properties.

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“…[103] Similarly, POMs are well-established light-driven catalysts with photoactivity in the UV and visible spectral range, with applications ranging from light-driven organic substrate oxidation to water oxidation and hydrogen evolution. [47,85,104] Todate, only few examples of POM-SACs for light-driven catalysis have been reported. In a pioneering example, [105] Adapted with permission.…”

Section: Light-driven Catalysismentioning

confidence: 99%

Polyoxometalate‐Single Atom Catalysts (POM‐SACs) in Energy Research and Catalysis

Liu

Streb

2021

Advanced Energy Materials

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have only been explored since the early 21st century, mainly because their identification and characterization has been virtually impossible before, due to a lack of high-resolution instrumentation (such as electron or scanning probe microscopies). [1,4] Beyond classical heterogeneous SACs, much research has recently focused on developing molecular SAC model systems. Here, polyoxometalate-single atom catalysts (POM-SACs) are of enormous interest as these molecular metal oxides could form the link between molecularly well-defined prototypes and technologically relevant solid-state SACs. In this Review, we will provide a brief introduction into the current status in SACs chemistry. We then discuss pioneering studies as well as current research challenges in POM-SACs chemistry with an emphasis on sustainable energy research. Finally, we will identify future areas in POM-SAC research and highlight the bottlenecks which need to be overcome to further develop this field. Classical Single Atom Catalysts Common Anchoring Strategies and Applications of SACsSACs offer the ultimate atomic reactivity, as each single atom is interacting with its environment and can act as catalytic site. [7][8][9] The key to the successful preparation of SACs is to stabilize catalytic metal centers as individual atoms by utilizing hosts/supports featuring strong binding motifs (Figure 1). Early model systems included high specific surface area carbons, [10,11] metal oxides, [12,13] as well as materials with uniform pores and regular structures, such as zeolites, [14] metal organic frameworks (MOFs) [5,[14][15][16][17][18][19] and covalent organic frameworks (COFs). [20,21] Stabilization of single-atoms on supports requires a support-surface with specific anchoring sites, such as coordinatively unsaturated surface atoms (e.g., O 2− , OH − ), surface vacancies or heteroatom dopants (e.g., N, P, S, and halogens). The SACs can be stabilized on the support surface by covalent or ionic interactions, or by geometric enclosure in small pores. Each anchoring mode offers several benefits and challenges. For instance, the coordination of a single metal atom to surface oxo ligands makes the single-atom accessible from the outside, e.g., for binding of a substrate. However, it also leads to high surface-energy and destabilization of the single-atom, so that leaching, or agglomeration are possible. In contrast, Single atom catalysts-SACs-have received intense interest in sustainable energy research due to their enormous application potential and broad catalytic scope. In particular, SACs anchored on molecular metal oxides-polyoxometalates (POMs)-offer unrivalled possibilities as models to understand the function of these complex systems on the atomic level. Research questions which are difficult to address for classical heterogeneous SACs can be addressed by experiment and theory using POM-SACs as prototype catalysts. This review reviews the emerging field of POM-SAC research with a focus on fundamental properties and their application in energy conversion...

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An unprecedented {Ni₁₄SiW₉} hybrid polyoxometalate with high photocatalytic hydrogen evolution activity

Abstract: A unique polyoxometalate with 14 nickel and 9 tungsten ions catalyses the reduction of protons under visible light.

Cited by 55 publications

References 25 publications

Phosphate‐Templated Encapsulation of a {Co^II₄O₄} Cubane in Germanotungstates as Carbon‐Free Homogeneous Water Oxidation Photocatalysts

Phosphate‐Templated Encapsulation of a {Co^II₄O₄} Cubane in Germanotungstates as Carbon‐Free Homogeneous Water Oxidation Photocatalysts

Recent Advances in First‐Row Transition Metal Clusters for Photocatalytic Water Splitting

Polyoxometalate‐Single Atom Catalysts (POM‐SACs) in Energy Research and Catalysis

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An unprecedented {Ni14SiW9} hybrid polyoxometalate with high photocatalytic hydrogen evolution activity

Abstract: A unique polyoxometalate with 14 nickel and 9 tungsten ions catalyses the reduction of protons under visible light.

Cited by 55 publications

References 25 publications

Phosphate‐Templated Encapsulation of a {CoII4O4} Cubane in Germanotungstates as Carbon‐Free Homogeneous Water Oxidation Photocatalysts

Phosphate‐Templated Encapsulation of a {CoII4O4} Cubane in Germanotungstates as Carbon‐Free Homogeneous Water Oxidation Photocatalysts

Recent Advances in First‐Row Transition Metal Clusters for Photocatalytic Water Splitting

Polyoxometalate‐Single Atom Catalysts (POM‐SACs) in Energy Research and Catalysis

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An unprecedented {Ni₁₄SiW₉} hybrid polyoxometalate with high photocatalytic hydrogen evolution activity

Phosphate‐Templated Encapsulation of a {Co^II₄O₄} Cubane in Germanotungstates as Carbon‐Free Homogeneous Water Oxidation Photocatalysts

Phosphate‐Templated Encapsulation of a {Co^II₄O₄} Cubane in Germanotungstates as Carbon‐Free Homogeneous Water Oxidation Photocatalysts