Interplay between the spin-selection rule and frontier orbital theory in O2 activation and CO oxidation by single-atom-sized catalysts on TiO2(110)

Literature Information

Publication Date 2016-08-09
DOI 10.1039/C6CP03168D
Impact Factor 3.676
Authors

Xingju Zhao, Jinlei Shi, Yu Jia, Zhengxiao Guo, Jun-Hyung Cho, Zhenyu Zhang


View Original

Abstract

Exploration of the catalytic activity of low-dimensional transition metal (TM) or noble metal catalysts is a vital subject of modern materials science because of their instrumental role in numerous industrial applications. Recent experimental advances have demonstrated the utilization of single atoms on different substrates as effective catalysts, which exhibit amazing catalytic properties such as more efficient catalytic performance and higher selectivity in chemical reactions as compared to their nanostructured counterparts; however, the underlying microscopic mechanisms operative in these single atom catalysts still remain elusive. Based on first-principles calculations, herein, we present a comparative study of the key kinetic rate processes involved in CO oxidation using a monomer or dimer of two representative TMs (Pd and Ni) on defective TiO2(110) substrates (TMn@TiO2(110), n = 1, 2) to elucidate the underlying mechanism of single-atom catalysis. We reveal that the O2 activation rates of the single atom TM catalysts deposited on TiO2(110) are governed cooperatively by the classic spin-selection rule and the well-known frontier orbital theory (or generalized d-band picture) that emphasizes the energy gap between the frontier orbitals of the TM catalysts and O2 molecule. We further illuminate that the subsequent CO oxidation reactions proceed via the Langmuir–Hinshelwood mechanism with contrasting reaction barriers for the Pd monomer and dimer catalysts. These findings not only provide an explanation for existing observations of distinctly different catalytic activities of Pd@TiO2(110) and Pd2@TiO2(110) [Kaden et al., Science, 2009, 326, 826–829] but also shed new insights into future utilization and optimization of single-atom catalysis.

Related Literature

Enhanced cytocompatibility and functional group content of poly(l-lysine) dendrimers by grafting with poly(oxazolines)

J. I. Hare, P. D. Kemmitt, K. E. Treacher, M. J. Waring, S. T. Barry, C. Alexander, M. Ashford

2016-05-20 Paper

DOI: 10.1039/C6PY00478D

Back cover

Cover

DOI: 10.1039/C7PY90057K

Synthesis of triphenylphosphine-based microporous organic nanotube framework supported Pd catalysts with excellent catalytic activity

Yang Xu, Tianqi Wang, Zidong He, Aiqing Zhong, Wei Yu, Buyin Shi, Kun Huang

2016-11-14 Paper

DOI: 10.1039/C6PY01706A

Straight chain D–A copolymers based on thienothiophene and benzothiadiazole for efficient polymer field effect transistors and photovoltaic cells

Yuxiang Li, Tack Ho Lee, Song Yi Park, Mohammad Afsar Uddin, Taehyo Kim, Sungu Hwang, Jin Young Kim, Han Young Woo

2016-06-15 Paper

DOI: 10.1039/C6PY00674D

Synthesis of random poly(hexyl thiophene-3-carboxylate) copolymers via oxidative direct arylation polymerization (oxi-DArP)

Nemal S. Gobalasingham, Robert M. Pankow, Barry C. Thompson

2017-03-02 Paper

DOI: 10.1039/C7PY00181A

Back cover

Cover

DOI: 10.1039/C6PY90156E

You might also like

Compound Q&A

What precautions should be taken when handling lithium chloride hydrate (1:1:1) (CAS: 16712-20-2)?

When handling lithium chloride hydrate (1:1:1) (CAS: 16712-20-2), it is importan...

16712-20-2Lithium chloride hyd...
Compound Q&A

Is 4-(4H-1,2,4-Triazol-4-yl)piperidine (CAS: 690261-92-8) safe?

4-(4H-1,2,4-Triazol-4-yl)piperidine is generally considered safe for use in phar...

690261-92-84-(4H-1,2,4-Triazol-...
Compound Q&A

How should waste containing 1,3-Thiazole-2-carboxamide (CAS: 16733-85-0) be handled?

Waste containing 1,3-Thiazole-2-carboxamide (CAS: 16733-85-0) should be collecte...

16733-85-01,3-Thiazole-2-carbo...
Compound Q&A

What regulatory guidelines apply to 5-(Difluoromethyl)-2-fluorobenzonitrile (CAS: 934175-58-3)?

5-(Difluoromethyl)-2-fluorobenzonitrile (CAS: 934175-58-3) is subject to regulat...

934175-58-35-(Difluoromethyl)-2...
Compound Q&A

How is Methyl 3-acetamido-2-thiophenecarboxylate (CAS: 22288-79-5) typically synthesized?

Methyl 3-acetamido-2-thiophenecarboxylate can be synthesized by the reaction of ...

22288-79-5Methyl 3-acetamido-2...
Compound Q&A

What is 4-Isoquinolinecarbonitrile (CAS: 34846-65-6)?

4-Isoquinolinecarbonitrile is a chemical compound with the CAS number 34846-65-6...

34846-65-64-Isoquinolinecarbon...
Compound Q&A

How should Methyl 1H-1,2,3-triazole-4-carboxylate (CAS: 877309-59-6) be stored?

Store Methyl 1H-1,2,3-triazole-4-carboxylate (CAS: 877309-59-6) in a cool, dry p...

877309-59-6Methyl 1H-1,2,3-tria...
Compound Q&A

What regulatory guidelines apply to 6-Bromo[1,3]thiazolo[5,4-b]pyridin-2-amine (CAS: 1160791-13-8)?

6-Bromo[1,3]thiazolo[5,4-b]pyridin-2-amine (CAS: 1160791-13-8) is subject to the...

1160791-13-86-Bromo[1,3]thiazolo...
Compound Q&A

Is (2S,3S)-2-Ammonio-3-(3,4-dihydroxyphenyl)-3-hydroxypropanoate (CAS: 23651-95-8) safe?

(2S,3S)-2-Ammonio-3-(3,4-dihydroxyphenyl)-3-hydroxypropanoate (CAS: 23651-95-8) ...

23651-95-8(2S,3S)-2-Ammonio-3-...
Compound Q&A

What are the physical and chemical properties of 7-bromo-3-methyl-3,4-dihydroquinazolin-4-one (CAS: 1293987-84-4)?

7-Bromo-3-methyl-3,4-dihydroquinazolin-4-one is a solid with a crystalline form....

1293987-84-47-bromo-3-methyl-3,4...

Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.