Abstract
Single atom catalysts (SACs) with metal1-Nx sites have shown promising activity and selectivity in direct catalytic oxidation of benzene to phenol. The reaction pathway is considered to be involving two steps, including a H2O2 molecule dissociated on the metal single site to form the (metal1-Nx)=O active site, and followed by the dissociation of another H2O2 on the other side of metal atom to form O=(metal1-Nx)=O intermediate center, which is active for the adsorption of benzene molecule via the formation of a C-O bond to form phenol. In this manuscript, we report a Cu SAC with nitrogen and oxygen dual-coordination (Cu1-N3O1 moiety) that doesn’t need the first H2O2 activation process, as verified by both experimental and density function theory (DFT) calculations results. Compared with the counterpart nitrogen-coordinated Cu SAC (denoted as Cu1/NC), Cu SAC with nitrogen and oxygen dual-coordination (denoted as Cu1/NOC) exhibits 2.5 times higher turnover frequency (TOF) and 1.6 times higher utilization efficiency of H2O2. Particularly, the coordination number (CN) of Cu atom in Cu1/NOC maintains four even after H2O2 treatment and reaction. Combining DFT calculations, the dynamic evolution of single atomic Cu with nitrogen and oxygen dual-coordination in hydroxylation of benzene is proposed. These findings provide an efficient route to improve the catalytic performance through regulating the coordination environments of SACs and demonstrate a new reaction mechanism in hydroxylation of benzene to phenol reaction.
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Yang, X. F.; Wang, A. Q.; Qiao, B. T.; Li, J.; Liu, J. Y.; Zhang, T. Single-atom catalysts: A new frontier in heterogeneous catalysis. Acc. Chem. Res. 2013, 46, 1740–1748.
Wang, A. Q.; Li, J.; Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2018, 2, 65–81.
Kaiser, S. K.; Chen, Z. P.; Faust Akl, D.; Mitchell, S.; Pérez-Ramirez, J. Single-atom catalysts across the periodic table. Chem. Rev. 2020, 120, 11703–11809.
Wang, Y.; Mao, J.; Meng, X. G.; Yu, L.; Deng, D. H.; Bao, X. H. Catalysis with two-dimensional materials confining single atoms: Concept, design, and applications. Chem. Rev. 2019, 119, 1806–1854.
Fei, H. L.; Dong, J. C.; Feng, Y. X.; Allen, C. S.; Wan, C. Z.; Volosskiy, B.; Li, M. F.; Zhao, Z. P.; Wang, Y. L.; Sun, H. T. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 2018, 1, 63–72.
Xi, W.; Wang, K.; Shen, Y. L.; Ge, M. K.; Deng, Z. L.; Zhao, Y. F.; Cao, Q. E.; Ding, Y.; Hu, G. Z.; Luo, J. Dynamic co-catalysis of Au single atoms and nanoporous Au for methane pyrolysis. Nat. Commun. 2020, 11, 1919.
Cao, L. N.; Liu, W.; Luo, Q. Q.; Yin, R. T.; Wang, B.; Weissenrieder, J.; Soldemo, M.; Yan, H.; Lin, Y.; Sun, Z. H. et al. Atomically dispersed iron hydroxide anchored on Pt for preferential oxidation of CO in H2. Nature 2019, 565, 631–635.
Li, X. Y.; Rong, H. P.; Zhang, J. T.; Wang, D. S.; Li, Y. D. Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance. Nano Res. 2020, 13, 1842–1855.
Xiong, Y.; Sun, W. M.; Han, Y. H.; Xin, P. Y.; Zheng, X. S.; Yan, W. S.; Dong, J. C.; Zhang, J.; Wang, D. S.; Li, Y. D. Cobalt single atom site catalysts with ultrahigh metal loading for enhanced aerobic oxidation of ethylbenzene. Nano Res. 2021, 14, 2418–2423.
Zitolo, A.; Goellner, V.; Armel, V.; Sougrati, M. T.; Mineva, T.; Stievano, L.; Fonda, E.; Jaouen, F. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 2015, 14, 937–942.
Yang, J. R.; Li, W. H.; Wang, D. S.; Li, Y. D. Single-atom materials: Small structures determine macroproperties. Small Struct. 2021, 2, 2000051.
Liu, J.; Cao, C. Y.; Liu, X. Z.; Zheng, L. R.; Yu, X. H.; Zhang, Q. H.; Gu, L.; Qi, R. L.; Song, W. G. Direct observation of metal oxide nanoparticles being transformed into metal single atoms with oxygen-coordinated structure and high-loadings. Angew. Chem., Int. Ed. 2021, 60, 15248–15253.
Mondelli, C.; Gözaydin, G.; Yan, N.; Pérez-Ramírez, J. Biomass valorisation over metal-based solid catalysts from nanoparticles to single atoms. Chem. Soc. Rev. 2020, 41, 3764–3782.
He, Y.; Liu, J. C.; Luo, L. L.; Wang, Y. G.; Zhu, J. F.; Du, Y. G.; Li, J.; Mao, S. X.; Wang, C. M. Size-dependent dynamic structures of supported gold nanoparticles in CO oxidation reaction condition. Proc. Natl. Acad. Sci. USA 2018, 115, 7700–7705.
Ding, S. P.; Hülsey, M. J.; Pérez-Ramírez, J.; Yan, N. Transforming energy with single-atom catalysts. Joule 2019, 3, 2897–2929.
Corma, A.; Concepción, P.; Boronat, M.; Sabater, M. J.; Navas, J.; Yacaman, M. J.; Larios, E.; Posadas, A.; López-Quintela, M. A.; Buceta, D. et al. Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity. Nat. Chem. 2013, 5, 775–781.
Li, H. L.; Wang, M. L.; Luo, L. H.; Zeng, J. Static regulation and dynamic evolution of single-atom catalysts in thermal catalytic reactions. Adv. Sci. 2019, 6, 1801471.
Wang, Y. G.; Mei, D. H.; Glezakou, V. A.; Li, J.; Rousseau, R. Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles. Nat. Commun. 2015, 6, 6511.
Liu, L. C.; Zakharov, D. N.; Arenal, R.; Concepcion, P.; Stach, E. A.; Corma, A. Evolution and stabilization of subnanometric metal species in confined space by in situ TEM. Nat. Commun. 2018, 9, 574.
Zhang, L. W.; Long, R.; Zhang, Y. M.; Duan, D. L.; Xiong, Y. J.; Zhang, Y. J.; Bi, Y. P. Direct observation of dynamic bond evolution in single-atom Pt/C3N4 catalysts. Angew. Chem., Int. Ed. 2020, 59, 6224–6229.
Schmidt, R. J. Industrial catalytic processes-phenol production. Appl. Catal. A:Gen. 2005, 280, 89–103.
Zakoshansky, V. M. The cumene process for phenol-acetone production. Petrol. Chem. 2007, 47, 273–284.
Mancuso, A.; Sacco, O.; Sannino, D.; Venditto, V.; Vaiano, V. One-step catalytic or photocatalytic oxidation of benzene to phenol: Possible alternative routes for phenol synthesis? Catalysts 2020, 10, 1424.
Deng, D. H.; Chen, X. Q.; Yu, L.; Wu, X.; Liu, Q. F.; Liu, Y.; Yang, H. X.; Tian, H. F.; Hu, Y. F.; Du, P. P. et al. A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature. Sci. Adv. 2015, 1, e1500462.
Zhang, M. L.; Wang, Y. G.; Chen, W. X.; Dong, J. C.; Zheng, L. R.; Luo, J.; Wan, J. W.; Tian, S. B.; Cheong, W. C.; Wang, D. S. et al. Metal (hydr)oxides@polymer core–shell strategy to metal single-atom materials. J. Am. Chem. Soc. 2017, 139, 10976–10979.
Zhu, Y. Q.; Sun, W. M.; Luo, J.; Chen, W. X.; Cao, T.; Zheng, L. R.; Dong, J. C.; Zhang, J.; Zhang, M. L.; Han, Y. H. et al. A cocoon silk chemistry strategy to ultrathin N-doped carbon nanosheet with metal single-site catalysts. Nat. Commun. 2018, 9, 3861.
Zhang, T.; Zhang, D.; Han, X. H.; Dong, T.; Guo, X. W.; Song, C. S.; Si, R.; Liu, W.; Liu, Y. F.; Zhao, Z. K. Preassembly strategy to fabricate porous hollow carbonitride spheres inlaid with single Cu-N3 sites for selective oxidation of benzene to phenol. J. Am. Chem. Soc. 2018, 140, 16936–16940.
Zhang, T.; Nie, X. W.; Yu, W. W.; Guo, X. W.; Song, C. S.; Si, R.; Liu, Y. F.; Zhao, Z. K. Single atomic Cu-N2 catalytic sites for highly active and selective hydroxylation of benzene to phenol. iScience 2019, 22, 97–108.
Pan, Y.; Chen, Y. J.; Wu, K. L.; Chen, Z.; Liu, S. J.; Cao, X.; Cheong, W. C.; Meng, T.; Luo, J.; Zheng, L. R. et al. Regulating the coordination structure of single-atom Fe-NxCy catalytic sites for benzene oxidation. Nat. Commun. 2019, 10, 4290.
Zhou, H.; Zhao, Y. F.; Gan, J.; Xu, J.; Wang, Y.; Lv, H. W.; Fang, S.; Wang, Z. Y.; Deng, Z. L.; Wang, X. Q. et al. Cation-exchange induced precise regulation of single copper site triggers room-temperature oxidation of benzene. J. Am. Chem. Soc. 2020, 142, 12643–12650.
Shang, H. S.; Zhou, X. Y.; Dong, J. C.; Li, A.; Zhao, X.; Liu, Q. H.; Lin, Y.; Pei, J. J.; Li, Z.; Jiang, Z. L. et al. Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity. Nat. Commun. 2020, 11, 3049.
Wang, X. Q.; Chen, Z.; Zhao, X. Y.; Yao, T.; Chen, W. X.; You, R.; Zhao, C. M.; Wu, G.; Wang, J.; Huang, W. X. et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO2. Angew. Chem., Int. Ed. 2018, 57, 1944–1948.
Hou, Y.; Qiu, M.; Kim, M. G.; Liu, P.; Nam, G.; Zhang, T.; Zhuang, X. D.; Yang, B.; Cho, J.; Chen, M. W. et al. Atomically dispersed nickel-nitrogen-sulfur species anchored on porous carbon nanosheets for efficient water oxidation. Nat. Commun. 2019, 10, 1392.
Liu, J.; Liu, Y.; Liu, N. Y.; Han, Y. Z.; Zhang, X.; Huang, H.; Lifshitz, Y.; Lee, S. T.; Zhong, J.; Kang, Z. H. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway. Science 2015, 347, 970–974.
Ravel, B.; Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: Data analysis for X-ray absorption spectroscopy using IEEFFTT. J. Synchrotron Rad. 2005, 12, 537–541.
Koningsberger, D. C.; Prins, R. X-ray Absorption: Pricciples, Applications, Techniques of EXAFS, SEXAFS and XANES; Wiley: New York, 1988.
Rehr, J. J.; Albers, R. C. Theoretical approaches to X-ray absorption fine structure. Rev. Mod. Phys. 2000, 72, 621–654.
Della Longa, S.; Arcovito, A.; Girasole, M.; Hazemann, J. L.; Benfatto, M. Quantitative analysis of X-ray absorption near edge structure data by a full multiple scattering procedure: The Fe-CO geometry in photolyzed carbonmonoxy-myoglobin single crystal. Phys. Rev. Lett. 2001, 87, 155501.
Cardelli, A.; Cibin, G.; Benfatto, M.; Della Longa, S.; Brigatti, M. F.; Marcelli, A. A crystal-chemical investigation of Cr substitution in muscovite by XANES spectroscopy. Phys. Chem. Miner. 2003, 30, 54–58.
Natoli, C. R.; Benfatto, M. A unifying scheme of interpretation of X-ray absorption spectra based on the multiple scattering theory. J Phys. Colloq. 1986, 47-11–23.
Wu, Z. Y.; Ouvrard, G.; Lemaux, S.; Moreau, P.; Gressier, P.; Lemoigno, F.; Rouxel, J. Sulfur K-edge X-ray absorption study of the charge transfer upon lithium intercalation into titanium disulfide. Rhys. Rev. Lett. 1996, 77, 2101–2104.
Kresse, G.; Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 1993, 47, 558–561.
Kresse, G.; Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Rhys. Rev. B 1994, 49, 14251–14269.
Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Perdew, J. P.; Burke, K.; Wang, Y. Generalized gradient approximation for the exchange-correlation hole of a many-electron system. Phys. Rev. B 1998, 57, 14999.
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188–5192.
Henkelman, G.; Uberuaga, B. P.; Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 2000, 113, 9901–9904.
Jorissen, K.; Rehr, J. J. New developments in FEFF: FEFF9 and JFEFF. J. Phys.:Conf. Ser. 2013, 430, 012001.
Xiong, Y.; Dong, J. C.; Huang, Z. Q.; Xin, P. Y.; Chen, W. X.; Wang, Y.; Li, Z.; Jin, Z.; Xing, W.; Zhuang, Z. B. et al. Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation. Nat. Nanotechnol. 2020, 15, 390–397.
Fei, H. L.; Dong, J. C.; Chen, D. L.; Hu, T. D.; Duan, X. D.; Shakir, I.; Huang, Y.; Duan, X. F. Single atom electrocatalysts supported on graphene or graphene-like carbons. Chem. Soc. Rev. 2019, 48, 5207–5241.
Wan, J. W.; Zhao, Z. H.; Shang, H. S.; Peng, B.; Chen, W. X.; Pei, J. J.; Zheng, L. R.; Dong, J. C.; Cao, R.; Sarangi, R. et al. In situ phosphatizing of triphenylphosphine encapsulated within metal–organic frameworks to design atomic Co1-P1N3 interfacial structure for promoting catalytic performance. J. Am. Chem. Soc. 2020, 142, 8431–8439.
Zhao, D.; Zhuang, Z. W.; Cao, X.; Zhang, C.; Peng, Q.; Chen, C.; Li, Y. D. Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation. Chem. Soc. Rev. 2020, 49, 2215–2264.
Fei, H. L.; Dong, J. C.; Arellano-Jiménez, M. J.; Ye, G. L.; Kim, N. D.; Samuel, E. L. G.; Peng, Z. W.; Zhu, Z.; Qin, F.; Bao, J. M. et al. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat. Commun. 2015, 6, 8668.
Zhang, J.; Wang, Z. Y.; Chen, W. X.; Xiong, Y.; Cheong, W. C.; Zheng, L. R.; Yan, W. S.; Gu, L.; Chen, C.; Peng, Q. et al. Tuning polarity of Cu-O bond in heterogeneous cu catalyst to promote additive-free hydroboration of alkynes. Chem 2020, 6, 725–737.
Zhang, J.; Zheng, C. Y.; Zhang, M. L.; Qiu, Y. J.; Xu, Q.; Cheong, W. C.; Chen, W. X.; Zheng, L. R.; Gu, L.; Hu, Z. P. et al. Controlling N-doping type in carbon to boost single-atom site Cu catalyzed transfer hydrogenation of quinoline. Nano Res. 2020, 13, 3082–3087.
Chen, Y. J.; Ji, S. F.; Wang, Y. G.; Dong, J. C.; Chen, W. X.; Li, Z.; Shen, R. A.; Zheng, L. R.; Zhuang, Z. B.; Wang, D. S. et al. Isolated single iron atoms anchored on N-doped porous carbon as an efficient electrocatalyst for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2017, 56, 6937–6941.
Acknowledgements
We thank the National Key R&D Program of China (Nos. 2018YFA0703503 and 2018YFA0208504), the National Natural Science Foundation of China (No. 21932006) and the Youth Innovation Promotion Association of CAS (No. 2017049) for financial support. We thank the beamline 1W1B station in Beijing Synchrotron Radiation Facility (BSRF) and Dr. Lirong Zheng for help in XAFS characterization.
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Dynamic evolution of nitrogen and oxygen dual-coordinated single atomic copper catalyst during partial oxidation of benzene to phenol
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Chen, W., Jin, H., He, F. et al. Dynamic evolution of nitrogen and oxygen dual-coordinated single atomic copper catalyst during partial oxidation of benzene to phenol. Nano Res. 15, 3017–3025 (2022). https://doi.org/10.1007/s12274-021-3936-4
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DOI: https://doi.org/10.1007/s12274-021-3936-4