Molecular Catalytic Kinetics Concepts

Santen, Rutger A. van

doi:10.1002/9783527630882.ch1

Cited by 9 publications

(5 citation statements)

References 27 publications

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“…According to this principle, the rate of catalytic reaction has a maximum when the rate of activation and the rate of product desorption balance. In this work, the balance could be around 50 °C, at which the maximum in the volcano plot was reached …”

Section: Resultsmentioning

confidence: 88%

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Bacterial Cellulose Supported Gold Nanoparticles with Excellent Catalytic Properties

Chen

Kang

Gong

et al. 2015

ACS Appl. Mater. Interfaces

182

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Amidoxime surface functionalized bacterial cellulose (AOBC) has been successfully prepared by a simple two-step method without obviously changing the morphology of bacterial cellulose. AOBC has been used as the reducing agent and carrier for the synthesis of gold nanoparticles (AuNPs) that distributed homogeneously on bacterial cellulose surface. Higher content in amidoxime groups in AOBC is beneficial for the synthesis of AuNPs with smaller and more uniform size. The AuNPs/AOBC nanohybrids have excellent catalytic activity for reduction of 4-nitrophenol (4-NP) by using NaBH4. It was found that catalytic activity of AuNPs/AOBC first increases with increasing NaBH4 concentration and temperature, and then leveled off at NaBH4 concentration above 238 mM and temperature above 50 °C. Moreover, AuNPs with smaller size have higher catalytic activity. The highest apparent turnover frequency of AuNPs/AOBC is 1190 h(-1). The high catalytic activity is due to the high affinity of 4-NP with AuNPs/AOBC and the reduced product 4-aminophenol has good solubility in water in the presence of AuNPs/AOBC. The catalytic stability of the AuNPs/AOBC was estimated by filling a fluid column contained AuNPs/AOBC and used for continuously catalysis of the reduction of 4-NP by using NaBH4. The column works well without detection of 4-NP in the eluent after running for more than two months, and it is still running. This work provides an excellent catalyst based on bacterial cellulose stabilized AuNPs and has promising applications in industry.

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Section: Resultsmentioning

confidence: 88%

“…Meanwhile, k app reached the biggest value at 50 °C (Figure b, inset). The heterogeneous catalytic reactions generally follow the Sabatier principle, the key molecular principle of catalysis . The substrate molecules have to adsorb to the catalyst and become activated, and the product molecules have to desorb.…”

Section: Resultsmentioning

confidence: 99%

Bacterial Cellulose Supported Gold Nanoparticles with Excellent Catalytic Properties

Chen

Kang

Gong

et al. 2015

ACS Appl. Mater. Interfaces

182

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“…A large negative value of E ads indicates a strong adsorption energy, and vice versa. Activation energy ( E a ) and apparent activation energy ( E aa ) of methane were calculated according to the following equations. , Apparent activation is the true activation energy reduced by adsorption energy of the reactant. , and where E TS is the total energy of the TS.…”

Section: Methodsmentioning

confidence: 99%

Methane Activation at the Metal–Support Interface of Ni₄–CeO₂(111) Catalyst: A Theoretical Study

et al. 2019

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Methane activation is usually assumed to take place on top of metal surfaces or metal clusters. It can also occur at the metal−support interface in metal-supported catalysts with reducible oxides, such as CeO 2 . In the present work, we exploit density functional theory with an additional Hubbard-like parameter (DFT + U) to calculate the activation of methane at an O site interfacing a Ni 4 metal cluster on a support, CeO 2 (111) surface. Two reaction routes, namely, radical and nonradical routes, are taken into account. We show that the nonradical route is favored with an apparent activation energy of 18.1 kcal/mol, which is lower than that for the radical route by 15.0 kcal/mol. In the nonradical route, the formation of a four-centered transition-state structure is observed while a C−H bond of methane is being cleaved to form an OH moiety and a CH 3 fragment that is being bound to the interfacial Ni atom. It is also found that the interfacial O atoms are out of the CeO 2 surface plane with Ce−O bond distances being much longer than those in the crystalline bulk CeO 2 , which allows them to be easily reduced, and hence, the interfacial O atoms become more reactive toward methane, as compared to the surface O atoms. The interactions between Ni 4 cluster and the CeO 2 (111) surface result in the reduction of two Ce 4+ ions to Ce 3+ , improving the reducibility of the interfacial O atoms. This should be an important key to the facile methane activation.

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“…Recent works show ML can be integrated with QM methods to overcome the computational bottleneck of pure QM modeling strategies and enable accurate screening of large alloy catalyst spaces . For example, using Bayesian linear regression (trained on DFT‐computed adsorption energies) and Brønsted−Evans−Polanyi relations (which relates the enthalpy of reaction to the activation energy), the effects of alloy composition, nanoparticle size, and surface segregation on NO decomposition turnover frequency (TOF) by Rh (1− x ) Au x nanoparticles were explored, Figure . SOAP (smooth overlap atomic position) was used as the kernel in their Bayesian linear regression scheme to approximate the similarity between two local atomic environments based on overlap integrals of three‐dimensional atomic distributions .…”

Section: Impact Of Machine Learning On Heterogeneous Catalysismentioning

confidence: 99%

Machine learning for heterogeneous catalyst design and discovery

et al. 2018

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Molecular Catalytic Kinetics Concepts

Cited by 9 publications

References 27 publications

Bacterial Cellulose Supported Gold Nanoparticles with Excellent Catalytic Properties

Bacterial Cellulose Supported Gold Nanoparticles with Excellent Catalytic Properties

Methane Activation at the Metal–Support Interface of Ni₄–CeO₂(111) Catalyst: A Theoretical Study

Machine learning for heterogeneous catalyst design and discovery

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Molecular Catalytic Kinetics Concepts

Cited by 9 publications

References 27 publications

Bacterial Cellulose Supported Gold Nanoparticles with Excellent Catalytic Properties

Bacterial Cellulose Supported Gold Nanoparticles with Excellent Catalytic Properties

Methane Activation at the Metal–Support Interface of Ni4–CeO2(111) Catalyst: A Theoretical Study

Machine learning for heterogeneous catalyst design and discovery

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Methane Activation at the Metal–Support Interface of Ni₄–CeO₂(111) Catalyst: A Theoretical Study