Universal strategy engineering grain boundaries for catalytic oxidative desulfurization

Xiong, Jun; Li, Jiayu; Chen, Chao; Jiang, Wei; Zhu, Wenshuai; Li, Huaming; Di, Jun

doi:10.1016/j.apcatb.2022.121714

Cited by 36 publications

(9 citation statements)

References 49 publications

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“…Moreover, electron paramagnetic resonance (EPR) as a meaningful tool was performed to further prove the formation of oxygen vacancies. Significantly, a new strong characteristic signal located at g = 2.003 is observed in the case of YS-V O -NMO, while NMO exhibits almost no prominent electron spin resonance (ESR) signal (Figure d) . This phenomenon agrees with XPS analysis that numerous oxygen vacancies with coordination-unsaturated sites are induced by the acid-assisted defect engineering.…”

Section: Resultsmentioning

confidence: 98%

Boosting Catalytic Oxidative Desulfurization Performance over Yolk–Shell Nickel Molybdate Fabricated by Defect Engineering

et al. 2023

Inorg. Chem.

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Developing catalysts with optimized surface properties is significant for advanced catalysis. Herein, a rational architectural design is proposed to successfully synthesize yolk–shell nickel molybdate with abundant oxygen vacancies (YS-VO-NMO) via an acid-assisted defect engineering strategy. Notably, YS-VO-NMO with the yolk–shell structure shows complex nanoconfined interior space, which is beneficial to the mass transfer and active sites exposure. Moreover, the defect engineering strategy is of great importance to modulate the surface electronic structure and atomic composition, which contributes to the enrichment of oxygen vacancies. Benefiting from these features, the higher hydrogen peroxide activation is achieved by YS-VO-NMO to produce more hydroxyl radicals compared with untreated nickel molybdate. Consequently, the defect-engineered YS-VO-NMO not only features superior catalytic activity (99.5%) but also retains high desulfurization efficiency after recycling eight times. This manuscript provides new inspiration for designing more promising defective materials via defect engineering and architecture for different applications besides oxidative desulfurization.

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Section: Resultsmentioning

confidence: 98%

Boosting Catalytic Oxidative Desulfurization Performance over Yolk–Shell Nickel Molybdate Fabricated by Defect Engineering

et al. 2023

Inorg. Chem.

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“…These grain boundaries are highly reactive sites for the hydrogen evolution reaction. Additionally, seed-induced two-step growth may also be effective to engineer grain boundaries into other metal oxides . Apart from materials growth to build grain boundaries, matrix induction can also engineer single atoms or single-metal-atom chains. ,, …”

Section: Defect Controlling Formation Strategies In 2d Atomic Layersmentioning

confidence: 99%

Defect Chemistry in 2D Atomic Layers for Energy Photocatalysis

Di,

Hao,

Jiang

et al. 2023

Acc. Mater. Res.

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Conspectus Photocatalysis is a promising technology to simultaneously relieve the worldwide energy crisis and environmental pollution issues, providing an effective avenue for carbon neutrality. Numerous efforts have been dedicated to the reasonable design of photocatalytic materials to improve the photocatalytic efficiency. Among these, building two-dimensional (2D) atomic layers with suitable energy band structure offers an alternative configuration to optimize bulk charge separation and surface reactions at the same time. The limited thickness of the 2D atomic layer favors the rapid bulk charge migration to the surface, reducing the recombination of electron–hole pairs and boosting the bulk charge separation efficiency. Moreover, the 2D atomic layer configuration makes the surface atomic structure easily regulated, for example, engineering defects. In 2D atomic layers, even infinitesimal amounts of defects can unlock the great potential that exists for tailoring the carrier concentration, electronic states, spin nature, and so on. The specific defects can introduce defect energy levels into the band gap and extend the light absorption. The carrier dynamic can be regulated by the defects and optimize the charge separation efficiency. Moreover, these defect configurations provide specific reactive sites to bind with different molecules, tuning the intermediate formation and facilitating reaction progression. In this Account, we present the group’s recent research progress in search of defective 2D atomic layers for energy photocatalysis. We start with the classification of defects in the 2D atomic layers, such as anion vacancies, cation vacancies, vacancy associates, single atom doping, pits, amorphization, grain boundaries, and single-metal-atom chains. Then, different defect controlling formation strategies are introduced to engineer various defects in 2D atomic layers with an emphasis on formation principle, such as thickness controlling, curve controlling strategy, template directed strategy, etching strategy, and matrix induction. Additionally, the critical roles of defects for enhanced photocatalytic performance from different aspects are highlighted, including electronic structure tailoring, charge trapping, interface interaction strengthening, reactant adsorption and activation, molecular intermediate interaction force tuning, and reaction energy barriers and paths, to acquire the fundamental insight of the photocatalytic mechanism and elucidate the relationship between the defective local allocation and photocatalytic behavior. Finally, diversified energy-related photocatalytic applications over defective 2D atomic layers are discussed, such as water splitting, N2 reduction, and CO2 reduction. We hope that this Account can facilitate the development of defect chemistry in 2D atomic layers and realize high-efficiency photocatalysis.

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“…19,20 Almost all previous strategies for elevating ODS performance have focused on increasing the lipophilic property to improve the mass transfer of SCC and modifying the electronic structure to create efficient active sites. 21 However, for the ODS system using a H 2 O 2 oxidant, the excessive lipophilicity of the catalyst restricts access of H 2 O 2 to the active site, leading to minimal enhancement of catalytic activity. 11,22,23 Apparently, the key to improve ODS performance lies in the creation of a favorable local reaction environment that mitigates the activity discrepancy arising from water−oil twophase catalysis.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Mo-based heterogeneous catalysts have garnered significant attention in the oxidation of thiophenic sulfides. , While bulk molybdenum oxides have demonstrated unsatisfactory ODS catalytic activity, dispersing molybdenum oxides nanoparticles on appropriate supports, such as metal oxides, molecular sieves and carbon materials, has yielded a substantial enhancement in catalytic performance. , Carbon materials, particularly graphene and CNTs, are promising supports for Mo-based catalysts due to their large surface area and lipophilic properties, which facilitate optimal contact with SCC in the oil phase. , Moreover, heteroatom-doped carbon materials offer a unique electron-donating ability, which guarantees a constant electrons supply to the active sites . In fact, ODS reaction involves two different processes with changing time scales: (1) physicochemical processes around the catalyst (mass transfer) and (2) chemical process at the catalytic active sites. , Almost all previous strategies for elevating ODS performance have focused on increasing the lipophilic property to improve the mass transfer of SCC and modifying the electronic structure to create efficient active sites . However, for the ODS system using a H 2 O 2 oxidant, the excessive lipophilicity of the catalyst restricts access of H 2 O 2 to the active site, leading to minimal enhancement of catalytic activity. ,, Apparently, the key to improve ODS performance lies in the creation of a favorable local reaction environment that mitigates the activity discrepancy arising from water–oil two-phase catalysis.…”

Section: Introductionmentioning

confidence: 99%

Engineering a Local Hydrophilic Environment in Fuel Oil for Efficient Oxidative Desulfurization with Minimum H₂O₂ Oxidant

Chen,

Ren,

Wang

et al. 2023

ACS Catal.

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Oxidative desulfurization (ODS) using H 2 O 2 oxidant has emerged as a viable carbon-neutral way to produce premium-grade sulfur-free fuels, yet it currently suffers from overconsumption of oxidants and low efficiency for the immiscibility and high interfacial tension of water and oil. Here, we report efficient ODS using minimal H 2 O 2 oxidant without phase transfer agents. This is achieved by introducing organic modifiers (for example, etidronic acid (EA)) on molybdenum oxides anchored carbon nanotubes to dynamically activate Mo active sites and capture H 2 O 2 molecules. Such in situ generated local hydrophilicity depends on the electron-donating and hydrophilic −OH functional groups in EA, which can not only endow Mo active sites with high electron density for chemisorption of H 2 O 2 but also ensure the sufficient supply of H 2 O 2 . Combined with the substrate enrichment effect of hydrophobic porous carbon to sulfur contaminants, the efficient ODS reaction occurs at the solid−water−oil three-phase interface. The complete desulfurization was achieved within 10 min at 40 °C with an O/S ratio of 1, surpassing the optimum in the literature. This work unveils an avenue to improve ODS activity by harnessing the local reaction environment.

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Universal strategy engineering grain boundaries for catalytic oxidative desulfurization

Cited by 36 publications

References 49 publications

Boosting Catalytic Oxidative Desulfurization Performance over Yolk–Shell Nickel Molybdate Fabricated by Defect Engineering

Boosting Catalytic Oxidative Desulfurization Performance over Yolk–Shell Nickel Molybdate Fabricated by Defect Engineering

Defect Chemistry in 2D Atomic Layers for Energy Photocatalysis

Engineering a Local Hydrophilic Environment in Fuel Oil for Efficient Oxidative Desulfurization with Minimum H₂O₂ Oxidant

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Universal strategy engineering grain boundaries for catalytic oxidative desulfurization

Cited by 36 publications

References 49 publications

Boosting Catalytic Oxidative Desulfurization Performance over Yolk–Shell Nickel Molybdate Fabricated by Defect Engineering

Boosting Catalytic Oxidative Desulfurization Performance over Yolk–Shell Nickel Molybdate Fabricated by Defect Engineering

Defect Chemistry in 2D Atomic Layers for Energy Photocatalysis

Engineering a Local Hydrophilic Environment in Fuel Oil for Efficient Oxidative Desulfurization with Minimum H2O2 Oxidant

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Engineering a Local Hydrophilic Environment in Fuel Oil for Efficient Oxidative Desulfurization with Minimum H₂O₂ Oxidant