A strong Jahn–Teller distortion in Mn<sub>3</sub>O<sub>4</sub>–MnO heterointerfaces for enhanced silver catalyzed formaldehyde reforming into hydrogen

Yu, Xuehan; Qian, Kun; Du, Leilei; Zhang, Jiemei; Lu, Nan; Miao, Ziqiang; Li, Yuezhou; Kobayashi, Hisayoshi; Yan, Xiaoqing; Li, Renhong

doi:10.1039/d2se00436d

Cited by 11 publications

(7 citation statements)

References 72 publications

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“…Notably, a distinctive phase boundary around the vicinity of Pd nanoparticles was formed between Mn 3 O 4 and MnO, indicating that the hydrogen spillover at the Pd site leads to partial reduction of Mn 3 O 4 to MnO more easily. Meanwhile, the lattice distortion and roughness were detected near the boundary, which may be caused by the Jahn–Teller effect . More intense interface disorder can be found in Figure h.…”

Section: Resultsmentioning

confidence: 92%

“…Meanwhile, the lattice distortion and roughness were detected near the boundary, which may be caused by the Jahn−Teller effect. 36 More intense interface disorder can be found in Figure 1h. This strong interface reconstruction is believed to weaken the Mn−O bond and create more defects, which then facilitates the oxidation of HCHO.…”

Section: Morphological and Structural Characterizationsmentioning

confidence: 88%

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Formaldehyde Ambient-Temperature Decomposition over Pd/Mn₃O₄–MnO Driven by Active Sites’ Self-Tandem Catalysis

Liu,

Lu,

Jiao

et al. 2024

Environ. Sci. Technol.

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The widespread presence of formaldehyde (HCHO) pollutant has aroused significant environmental and health concerns. The catalytic oxidation of HCHO into CO 2 and H 2 O at ambient temperature is regarded as one of the most efficacious and environmentally friendly approaches; to achieve this, however, accelerating the intermediate formate species formation and decomposition remains an ongoing obstacle. Herein, a unique tandem catalytic system with outstanding performance in lowtemperature HCHO oxidation is proposed on well-structured Pd/Mn 3 O 4 − MnO catalysts possessing bifunctional catalytic centers. Notably, the optimized tandem catalyst achieves complete oxidation of 100 ppm of HCHO at just 18 °C, much better than the Pd/Mn 3 O 4 (30%) and Pd/MnO (27%) counterparts as well as other physical tandem catalysts. The operando analyses and physical tandem investigations reveal that HCHO is primarily activated to gaseous HCOOH on the surface of Pd/Mn 3 O 4 and subsequently converted to H 2 CO 3 on the Pd/MnO component for deep decomposition. Theoretical studies disclose that Pd/Mn 3 O 4 exhibits a favorable reaction energy barrier for the HCHO → HCOOH step compared to Pd/MnO; while conversely, the HCOOH → H 2 CO 3 step is more facilely accomplished over Pd/MnO. Furthermore, the nanoscale intimacy between two components enhances the mobility of lattice oxygen, thereby facilitating interfacial reconstruction and promoting interaction between active sites of Pd/Mn 3 O 4 and Pd/MnO in local vicinity, which further benefits sustained HCHO tandem catalytic oxidation. The tandem catalysis demonstrated in this work provides a generalizable platform for the future design of well-defined functional catalysts for oxidation reactions.

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Section: Resultsmentioning

confidence: 92%

Section: Morphological and Structural Characterizationsmentioning

confidence: 88%

Formaldehyde Ambient-Temperature Decomposition over Pd/Mn₃O₄–MnO Driven by Active Sites’ Self-Tandem Catalysis

Liu,

Lu,

Jiao

et al. 2024

Environ. Sci. Technol.

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“…Chief among these is the importance of JT effects for increasing the water oxidation activity of catalysts that include d 4 metal centers. This structure–property relationship is already well-known in heterogeneous catalysis, − , and it is high time it were applied to the development of molecular catalysts for artificial water splitting.…”

Section: Discussionmentioning

confidence: 90%

“…These effects have been noted to affect the structure and reactivity of the OEC as well as other synthetic catalysts containing d 4 metal centers; 29 − 39 JT effects have even been linked to increased water oxidation activity in heterogeneous catalysts. 42 − 44 , 51 In 3344-OAc , we found that JT effects play a pivotal role in multiple reaction steps. During activation, JT-elongated bonds provided key weak points for water attack and subsequent ligand exchange.…”

Section: Introductionmentioning

confidence: 85%

Regeneration and Degradation in a Biomimetic Polyoxometalate Water Oxidation Catalyst

2023

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Complete understanding of catalytic cycles is required to advance the design of water oxidation catalysts, but it is difficult to attain, due to the complex factors governing their reactivity and stability. In this study, we investigate the regeneration and degradation pathways of the highly active biomimetic water oxidation catalyst [Mn3+ 2Mn4+ 2V4O17(OAc)3]3–, thereby completing its catalytic cycle. Beginning with the deactivated species [Mn3+ 4V4O17(OAc)2]4– left over after O2 evolution, we scrutinize a network of reaction intermediates belonging to two alternative water oxidation cycles. We find that catalyst regeneration to the activated species [Mn4+ 4V4O17(OAc)2(OH)(H2O)]− proceeds via oxidation of each Mn center, with one water ligand being bound during the first oxidation step and a second water ligand being bound and deprotonated during the final oxidation step. ΔΔG values for this last oxidation are consistent with previous experimental results, while regeneration within an alternative catalytic cycle was found to be thermodynamically unfavorable. Extensive in silico sampling of catalyst structures also revealed two degradation processes: cubane opening and ligand dissociation, both of which have low barriers at highly reduced states of the catalyst due to the presence of Jahn–Teller effects. These mechanistic insights are expected to spur the development of more efficient and stable Mn cubane water oxidation catalysts.

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“…Taking β/δ-FeOOH as an example, there is 6-electron filling in the Fe 3d orbital of the single β-FeOOH phase and 7-electron filling in the Fe 3d orbital of the β/δ-FeOOH mixed phases (Figure e,f). According to the Jahn–Teller effect, an extra electron can be filled into the higher energy level e g orbital, which results in a large lattice distortion and more oxygen vacancies in β/δ-FeOOH mixed phases. , Ultimately, FeOOH with a mixed β/δ phase provides outstanding electrocatalytic OER activity attributed to the higher oxygen vacancy density and optimal electronic structure (Figure d) …”

Section: Metal Carbides Nitrides Borides and Hydroxidesmentioning

confidence: 99%

Crystal-Phase Engineering in Heterogeneous Catalysis

Zhao,

Wang,

Feng

et al. 2023

Chem. Rev.

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The performance of a chemical reaction is critically dependent on the electronic and/or geometric structures of a material in heterogeneous catalysis. Over the past century, the Sabatier principle has already provided a conceptual framework for optimal catalyst design by adjusting the electronic structure of the catalytic material via a change in composition. Beyond composition, it is essential to recognize that the geometric atomic structures of a catalyst, encompassing terraces, edges, steps, kinks, and corners, have a substantial impact on the activity and selectivity of a chemical reaction. Crystal-phase engineering has the capacity to bring about substantial alterations in the electronic and geometric configurations of a catalyst, enabling control over coordination numbers, morphological features, and the arrangement of surface atoms. Modulating the crystallographic phase is therefore an important strategy for improving the stability, activity, and selectivity of catalytic materials. Nonetheless, a complete understanding of how the performance depends on the crystal phase of a catalyst remains elusive, primarily due to the absence of a molecular-level view of active sites across various crystal phases. In this review, we primarily focus on assessing the dependence of catalytic performance on crystal phases to elucidate the challenges and complexities inherent in heterogeneous catalysis, ultimately aiming for improved catalyst design.

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A strong Jahn–Teller distortion in Mn₃O₄–MnO heterointerfaces for enhanced silver catalyzed formaldehyde reforming into hydrogen

Abstract: The Jahn-Teller effect has received intense interest in the field of catalysis because of its ability to optimize the surface electron state to tune the adsorption behavior of reactants on...

Cited by 11 publications

References 72 publications

Formaldehyde Ambient-Temperature Decomposition over Pd/Mn₃O₄–MnO Driven by Active Sites’ Self-Tandem Catalysis

Formaldehyde Ambient-Temperature Decomposition over Pd/Mn₃O₄–MnO Driven by Active Sites’ Self-Tandem Catalysis

Regeneration and Degradation in a Biomimetic Polyoxometalate Water Oxidation Catalyst

Crystal-Phase Engineering in Heterogeneous Catalysis

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A strong Jahn–Teller distortion in Mn3O4–MnO heterointerfaces for enhanced silver catalyzed formaldehyde reforming into hydrogen

Abstract: The Jahn-Teller effect has received intense interest in the field of catalysis because of its ability to optimize the surface electron state to tune the adsorption behavior of reactants on...

Cited by 11 publications

References 72 publications

Formaldehyde Ambient-Temperature Decomposition over Pd/Mn3O4–MnO Driven by Active Sites’ Self-Tandem Catalysis

Formaldehyde Ambient-Temperature Decomposition over Pd/Mn3O4–MnO Driven by Active Sites’ Self-Tandem Catalysis

Regeneration and Degradation in a Biomimetic Polyoxometalate Water Oxidation Catalyst

Crystal-Phase Engineering in Heterogeneous Catalysis

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Product

Resources

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A strong Jahn–Teller distortion in Mn₃O₄–MnO heterointerfaces for enhanced silver catalyzed formaldehyde reforming into hydrogen

Formaldehyde Ambient-Temperature Decomposition over Pd/Mn₃O₄–MnO Driven by Active Sites’ Self-Tandem Catalysis

Formaldehyde Ambient-Temperature Decomposition over Pd/Mn₃O₄–MnO Driven by Active Sites’ Self-Tandem Catalysis