Strategies for Perfect Confinement of POM@MOF and Its Applications in Producing Defect-Rich Electrocatalyst

Abstract

Polyoxometalate encapsulated by metal–organic framework (POM@MOF) hybrid is an ideal precursor for electrocatalysts because it provides a homogeneous catalyst system with a flexible synergistic effect. However, controlling its fine structures to activate the derived catalyst after pyrolysis remains a challenge. The uniformly distributed carbon-defect tungsten oxides on the 3D carbon matrix were synthesized by using phospho-tungstic acid confined in HKUST-1 (PA@HKUST-1) as the precursor. By choosing ethanol as the solvent, the framework of PA@HKUST-1 was retained integrally and each pore of HKUST-1 kept intact even with holding the PA molecule inside. The well-organized structure of PA@HKUST-1 facilitated to offer a highly distributed metal source, and further transform into defect-rich catalyst. The average size of the resulting WO x C y /C catalysts was 1.5 nm, which was similar to a single molecule of PA. The WO x C y /C catalysts exhibited superior activity in the methanol oxidation reaction after being platinized due to the enhanced resistance to CO poisoning, which is also confirmed by DFT. This finding suggests a new route to design and achieve the defect-rich catalyst with controllable size.

The fabrication of CuBTC@PW12 with prominent peroxidase-mimicking activity for colorimetric detection of H2O2 and ascorbic acid via “on–off” switch

“…22–25 Recently, POMOF composites have also been reported as enzyme mimics and exhibited good peroxidase-mimicking activity. 13,26–28 As expected, the high-performance colorimetric biosensor integrated the advantages of POMs and MOFs and overcomes their shortcomings synchronously. The POMOF nanoenzymes overcome the shortcomings of single MOF materials, and exhibited preferable catalytic performance due to their synergistic effect and more catalytically active sites, with outstanding performance compared to other 2D material-based nanozymes.…”

Efficient One‐Pot Synthesis of 2,5‐Furandicarboxylic Acid from Sugars over Polyoxometalate/Metal‐Organic Framework Catalysts

“…The micropores and mesopores dominated the structures of the catalysts [47] . After introducing the PW into the structure of UiO‐66, the BET surface area of PW/UiO was substantially reduced due to the partial occupation of the channels (Table S2) [48,49] . The PW/UiO(Zr, Co) presented a higher BET surface area than PW/UiO, which was attributed to the Co species bound to the framework.…”

“…[47] After introducing the PW into the structure of UiO-66, the BET surface area of PW/UiO was substantially reduced due to the partial occupation of the channels (Table S2). [48,49] The PW/UiO(Zr, Co) presented a higher BET surface area than PW/UiO, which was attributed to the Co species bound to the framework. After soaking the catalysts in water for a week, direct observation of PW/UiO(Zr, Co) did not reveal any color change.…”

Recent research progress on polyoxometalate-based electrocatalysts in energy generation

“…81 In POMsubstrate-based nanostructures, POMs can be incorporated into or onto various types of nanomaterials, such as metal nanoparticles, metal foam, metal oxides, metal suldes and metal carbides. [82][83][84][85][86] The incorporation of POMs in nanomaterials can provide unique properties and functionalities in the resulting hybrid materials. The abundant oxygen atoms in POMs synergize with nanomaterials, functioning as active sites for electrocatalytic reactions.…”