AI Chat Paper
Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
Search articles, authors, keywords, DOl and etc.
{{expandStatus?'Exit ':''}}Advanced Search
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.
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.; Gözaydın, G.; Yan, N.; Pérez-Ramírez, J. Biomass valorisation over metal-based solid catalysts from nanoparticles to single atoms. Chem. Soc. Rev. 2020, 49, 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 IFEFFIT. J. Synchrotron Rad. 2005, 12, 537–541.
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. Phys. 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. Phys. 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.
京公网安备11010802044758号