Evaluation of the degree of rate control via automatic differentiation

Yang, Yilin; Achar, Siddarth K.; Kitchin, John R.

doi:10.1002/aic.17653

Cited by 5 publications

(2 citation statements)

References 37 publications

(98 reference statements)

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“…Preliminary steps were done by performing a degree of rate control (DRC) analysis, but unfortunately we faced numerical instabilities with the evaluation of numerical derivatives. Finite difference method has already been reported problematic previously, [70] especially in transient kinetics where the magnitude of the finite-size perturbation can affect the convergence of the dynamic steady-state. [71] Besides, it is important to point out that Pt 4 Ge 3 will also get poisoned eventually at higher CO pressures.…”

Section: Microkinetic Simulationsmentioning

confidence: 99%

Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**

Ugartemendia,

Mercero,

de Cózar

et al. 2024

ChemCatChem

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Control of CO emissions raises serious environmental concerns in the current chemical industry, as well as in nascent technologies based on hydrogen such as electrolyzers and fuel cells. Pt remains one of the state‐of‐art catalysts for the CO oxidation reaction, but suffers from CO self–poisoning. Recently, PtGe alloys were proposed as an excellent alternative to reduce CO poisoning. In this work we investigate the impact of Ge content on the CO oxidation kinetics of P4Gen subnanoclusters supported on MgO. Pt−Ge nanoalloys act as a bifunctional catalyst by displaying dual adsorption sites; i.e., CO is adsorbed on Pt whereas oxygen binds to Ge, forming an alternative oxygen source GeOx. Besides, Ge alloying modifies the electronic structure of Pt (ligand effects) and reduces the affinity to CO. In this way, the competition between CO and O2 adsorption and the overbinding of CO is alleviated, achieving a CO poisoning−free kinetic regime. Our calculations suggest that Pt4Ge3 is the optimal catalyst, evidencing that alloying composition is a parameter of extreme importance in nanocatalyst design. The work relies on global optimization search techniques to determine the accessibility of multiple structures at different conditions, mechanistic studies and microkinetic modelling

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Section: Microkinetic Simulationsmentioning

confidence: 99%

Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**

Ugartemendia,

Mercero,

de Cózar

et al. 2024

ChemCatChem

View full text Add to dashboard Cite

show abstract

“…The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.4c00365. List of variables; complete microkinetic model equations and computational methods; brief literature review of kinetic scaling relations and barriers reported for the OER; method for estimating bounds of the reversible activation barrier; additional static catalyst simulation results; additional programmable catalyst simulation results; additional refs − (PDF) …”

mentioning

confidence: 99%

Dynamic Promotion of the Oxygen Evolution Reaction via Programmable Metal Oxides

Gathmann,

Bartel,

Grabow

et al. 2024

ACS Energy Lett.

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Hydrogen gas is a promising renewable energy storage medium when produced via water electrolysis, but this process is limited by the sluggish kinetics of the anodic oxygen evolution reaction (OER). Herein, we used a microkinetic model to investigate promoting the OER using programmable oxide catalysts (i.e., forced catalyst dynamics). We found that programmable catalysts could increase current density at a fixed overpotential (100−600× over static rates) or reduce the overpotential required to reach a fixed current density of 10 mA cm −2 (45−140% reduction vs static). In our kinetic parametrization, the key parameters controlling the quality of the catalytic ratchet were the O*-to-OOH* and O*-to-OH* activation barriers. Our findings indicate that programmable catalysts may be a viable strategy for accelerating the OER or enabling lower-overpotential operation, but a more accurate kinetic parametrization is required for precise predictions of performance, ratchet quality, and resulting energy efficiency.

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Optimization and Security Challenges in Cloud Computing within Big Data Enviro

Lin

2024

WJIMT

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As big data continues to proliferate at an unprecedented rate, cloud computing has emerged as a fundamental technology for managing, storing, and processing these vast datasets, with global data volumes projected to reach 175 zettabytes by 2025. Our study delves into the critical optimization strategies and security challenges that cloud computing systems face in big data environments. By employing advanced quantification methods, we demonstrate that cloud computing can achieve a 40% reduction in IT infrastructure costs and enhance data processing efficiency by 60%. However, these benefits are accompanied by significant security risks, including a 30% increase in data breaches due to centralized data storage and a 25% rise in data tampering incidents during transmission. To address these challenges, we propose a comprehensive framework that includes refined data screening mechanisms, capable of reducing data redundancy by up to 50%, and enhanced device security protocols to mitigate potential vulnerabilities. Additionally, we emphasize the critical role of optimizing information flow processing, which can achieve a 20% reduction in latency, thereby improving real-time data handling capabilities. Our study further advocates for the establishment of robust network security architectures, integrating cutting-edge encryption technologies and real-time threat monitoring systems, to safeguard data integrity and confidentiality in cloud environments. We conclude by outlining the imperative for ongoing research into AI-driven security enhancements and the formulation of global cybersecurity standards, essential for maintaining the resilience and efficiency of cloud computing systems in the era of big data.

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Evaluation of the degree of rate control via automatic differentiation

Cited by 5 publications

References 37 publications

Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**

Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**

Dynamic Promotion of the Oxygen Evolution Reaction via Programmable Metal Oxides

Optimization and Security Challenges in Cloud Computing within Big Data Enviro

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