Optimizing geometric configuration of single Zn-N₄ sites for boosting reciprocal transformation between aromatic alcohols and aldehydes

Sheldon, R. A.; Arends, I. W. C. E.; Ten Brink, G. J.; Dijksman. A. Green, catalytic oxidations of alcohols. Acc. Chem. Res. 2002, 35, 774–781.

Enache, D. I.; Edwards, J. K.; Landon, P.; Solsona-Espriu, B.; Carley, A. F.; Herzing, A. A.; Watanabe, M.; Kiely, C. J.; Knight, D. W.; Hutchings, G. J. Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO₂ catalysts. Science 2006, 311, 362–365.

Ji, S. F.; Chen, Y. J.; Zhang, Z. D.; Cheong, W. C.; Liu, Z. R.; Wang, D. S.; Li, Y. D. Single-atomic-site cobalt stabilized on nitrogen and phosphorus co-doped carbon for selective oxidation of primary alcohols. Nanoscale Horiz. 2019, 4, 902–906.

Bhanushali, J. T.; Kainthla, I.; Keri, R. S.; Nagaraja, B. M. Catalytic hydrogenation of benzaldehyde for selective synthesis of benzyl alcohol: A review. ChemistrySelect 2016, 1, 3839–3853.

Guo, Z.; Liu, B.; Zhang, Q. H.; Deng, W. P.; Wang, Y.; Yang, Y. H. Recent advances in heterogeneous selective oxidation catalysis for sustainable chemistry. Chem. Soc. Rev. 2014, 43, 3480–3524.

Pagliaro, M.; Campestrini, S.; Ciriminna, R. Ru-based oxidation catalysis. Chem. Soc. Rev. 2005, 34, 837–845.

Li, H.; Qin, F.; Yang, Z. P.; Cui, X. M.; Wang, J. F.; Zhang, L. Z. New reaction pathway induced by plasmon for selective benzyl alcohol oxidation on BiOCl possessing oxygen vacancies. J. Am. Chem. Soc. 2017, 139, 3513–3521.

Leithall, R. M.; Shetti, V. N.; Maurelli, S.; Chiesa, M.; Gianotti, E.; Raja, R. Toward understanding the catalytic synergy in the design of bimetallic molecular sieves for selective aerobic oxidations. J. Am. Chem. Soc. 2013, 135, 2915–2918.

Tanaka, A.; Hashimoto, K.; Kominami, H. Preparation of Au/CeO₂ exhibiting strong surface plasmon resonance effective for selective or chemoselective oxidation of alcohols to aldehydes or ketones in aqueous suspensions under irradiation by green light. J. Am. Chem. Soc. 2012, 134, 14526–14533.

Xin, P. Y.; Li, J.; Xiong, Y.; Wu, X.; Dong, J. C.; Chen, W. X.; Wang, Y.; Gu, L.; Luo, J.; Rong, H. P. et al. Revealing the active species for aerobic alcohol oxidation by using uniform supported palladium catalysts. Angew. Chem., Int. Ed. 2018, 57, 4642–4646.

Mori, K.; Hara, T.; Mizugaki, T.; Ebitani, K.; Kaneda, K. Hydroxyapatite-supported palladium nanoclusters: A highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen. J. Am. Chem. Soc. 2004, 126, 10657–10666.

Zhang, S. L.; Han, A. J.; Zhai, Y. L.; Zhang, J.; Cheong, W. C.; Wang, D. S.; Li, Y. D. ZIF-derived porous carbon supported Pd nanoparticles within mesoporous silica shells: Sintering- and leaching-resistant core–shell nanocatalysts. Chem. Commun. 2017, 53, 9490–9493.

Chen, Y. Z.; Wang, Z. U.; Wang, H. W.; Lu, J. L.; Yu, S. H.; Jiang, H. L. Singlet oxygen-engaged selective photo-oxidation over Pt nanocrystals/porphyrinic MOF: The roles of photothermal effect and Pt electronic state. J. Am. Chem. Soc. 2017, 139, 2035–2044.

Li, T. B.; Liu, F.; Tang, Y.; Li, L.; Miao, S.; Su, Y.; Zhang, J. Y.; Huang, J. H.; Sun, H.; Haruta, M. et al. Maximizing the number of interfacial sites in single-atom catalysts for the highly selective, solvent-free oxidation of primary alcohols. Angew. Chem., Int. Ed. 2018, 57, 7795–7799.

Guan, B. T.; Xing, D.; Cai, G. X.; Wan, X. B.; Yu, N.; Fang, Z.; Yang, L. P.; Shi, Z. J. Highly selective aerobic oxidation of alcohol catalyzed by a gold(I) complex with an anionic ligand. J. Am. Chem. Soc. 2005, 127, 18004–18005.

Ji, S. F.; Chen, Y. J.; Fu, Q.; Chen, Y. F.; Dong, J. C.; Chen, W. X.; Li, Z.; Wang, Y.; Gu, L.; He, W. et al. Confined pyrolysis within metal-organic frameworks to form uniform Ru₃ clusters for efficient oxidation of alcohols. J. Am. Chem. Soc. 2017, 139, 9795–9798.

Dijksman, A.; Marino-González, A.; Mairata i Payeras, A.; Arends, I. W. C. E.; Sheldon, R. A. Efficient and selective aerobic oxidation of alcohols into aldehydes and ketones using ruthenium/TEMPO as the catalytic system. J. Am. Chem. Soc. 2001, 123, 6826–6833.

Zhan, B. Z.; White, M. A.; Sham, T. K.; Pincock, J. A.; Doucet, R. J.; Rao, K. V. R.; Robertson, K. N.; Cameron, T. S. Zeolite-confined nano-RuO₂: A green, selective, and efficient catalyst for aerobic alcohol oxidation. J. Am. Chem. Soc. 2003, 125, 2195–2199.

Wang, D.; Astruc, D. The golden age of transfer hydrogenation. Chem. Rev. 2015, 115, 6621–6686.

Tian, S. B.; Wang, Z. Y.; Gong, W. B.; Chen, W. X.; Feng, Q. C.; Xu, Q.; Chen, C.; Chen, C.; Peng, Q.; Gu, L. et al. Temperature-controlled selectivity of hydrogenation and hydrodeoxygenation in the conversion of biomass molecule by the Ru₁/mpg-C₃N₄ catalyst. J. Am. Chem. Soc. 2018, 140, 11161–11164.

Li, W. H.; Yang, J. R.; Wang, D. S. Long-range interactions in diatomic catalysts boosting electrocatalysis. Angew. Chem., Int. Ed. 2022, 61, e202213318.

Zhu, P.; Xiong, X.; Wang, D. S. Regulations of active moiety in single atom catalysts for electrochemical hydrogen evolution reaction. Nano Res. 2022, 15, 5792–5815.

Li, R. Z.; Wang, D. S. Understanding the structure–performance relationship of active sites at atomic scale. Nano Res. 2022, 15, 6888–6923.

Zheng, X. B.; Li, B. B.; Wang, Q. S.; Wang, D. S.; Li, Y. D. Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis. Nano Res. 2022, 15, 7806–7839.

Zhang, Z. D.; Zhu, J. X.; Chen, S. H.; Sun, W. M.; Wang, D. S. Liquid fluxional Ga single atom catalysts for efficient electrochemical CO₂ reduction. Angew. Chem., Int. Ed. 2023, 62, e202215136.

Yang, J. R.; Li, W. H.; Xu, K. N.; Tan, S. D.; Wang, D. S.; Li, Y. D. Regulating the tip effect on single-atom and cluster catalysts: Forming reversible oxygen species with high efficiency in chlorine evolution reaction. Angew. Chem., Int. Ed. 2022, 61, e202200366.

Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater. 2022, 1, 100013.

Wang, Q. Y.; Dong, L. Y.; Li, M. Z.; Lu, H. L.; Wei, G. D.; Qu, Y.; Wang, G. F. Z-scheme heterojunction photocatalyst based on lanthanum single-atom anchored on black phosphorus for regulating surface active sites, therefore enhancing photocatalytic CO₂ reduction with ≈ 100% CO selectivity. Adv. Funct. Mater. 2022, 32, 2207330.

Bao, S.; Yu, H. Y.; Gao, G. Y.; Zhu, H. Y.; Wang, D. S.; Zhu, P. F.; Wang, G. F. Rare-earth single atom based luminescent composite nanomaterials: Tunable full-color single phosphor and applications in WLEDs. Nano Res. 2022, 15, 3594–3605.

Qin, J. Y.; Liu, H.; Zou, P. C.; Zhang, R.; Wang, C. Y.; Xin, H. L. Altering ligand fields in single-atom sites through second-shell anion modulation boosts the oxygen reduction reaction. J. Am. Chem. Soc. 2022, 144, 2197–2207.

Jin, J.; Han, X.; Fang, Y. Y.; Zhang, Z. D.; Li, Y. P.; Zhang, T. Y.; Han, A. J.; Liu, J. F. Microenvironment engineering of Ru single-atom catalysts by regulating the cation vacancies in NiFe-layered double hydroxides. Adv. Funct. Mater. 2022, 32, 2109218.

Tiburcio, E.; Greco, R.; Mon, M.; Ballesteros-Soberanas, J.; Ferrando-Soria, J.; López-Haro, M.; Hernández-Garrido, J. C.; Oliver-Meseguer, J.; Marini, C.; Boronat, M. et al. Soluble/MOF-supported palladium single atoms catalyze the ligand-, additive-, and solvent-free aerobic oxidation of benzyl alcohols to benzoic acids. J. Am. Chem. Soc. 2021, 143, 2581–2592.

Chen, Y. J.; Wang, P. X.; Hao, H. G.; Hong, J. J.; Li, H. J.; Ji, S. F.; Li, A.; Gao, R.; Dong, J. C.; Han, X. D. et al. Thermal atomization of platinum nanoparticles into single atoms: An effective strategy for engineering high-performance nanozymes. J. Am. Chem. Soc. 2021, 143, 18643–18651.

Shan, J. Q.; Ye, C.; Chen, S. M.; Sun, T. L.; Jiao, Y.; Liu, L. M.; Zhu, C. Z.; Song, L.; Han, Y.; Jaroniec, M. et al. Short-range ordered iridium single atoms integrated into cobalt oxide spinel structure for highly efficient electrocatalytic water oxidation. J. Am. Chem. Soc. 2021, 143, 5201–5211.

Huang, Q. E.; Wang, B. L.; Ye, S.; Liu, H.; Chi, H. B.; Liu, X. Y.; Fan, H. J.; Li, M. R.; Ding, C. M.; Li, Z. et al. Relation between water oxidation activity and coordination environment of C, N-coordinated mononuclear Co catalyst. ACS Catal. 2022, 12, 491–496.

Feng, Y. C.; Long, S. S.; Chen, B. L.; Jia, W. L.; Xie, S. J.; Sun, Y.; Tang, X.; Yang, S. L.; Zeng, X. H.; Lin. L. Inducing electron dissipation of pyridinic N enabled by single Ni-N₄ sites for the reduction of aldehydes/ketones with ethanol. ACS Catal. 2021, 11, 6398–6405.

Liang, J. L.; Song, Q. Q.; Wu, J. H.; Lei, Q.; Li, J.; Zhang, W.; Huang, Z. M.; Kang, T. X.; Xu, H.; Wang, P. et al. Anchoring copper single atoms on porous boron nitride nanofiber to boost selective reduction of nitroaromatics. ACS Nano 2022, 16, 4152–4161.

Liu, J. B.; Wang, D. S.; Huang, K.; Dong, J. C.; Liao, J. W.; Dai, S.; Tang, X.; Yan, M. M.; Gong, H. S.; Liu, J. J. et al. Iodine-doping-induced electronic structure tuning of atomic cobalt for enhanced hydrogen evolution electrocatalysis. ACS Nano 2021, 15, 18125–18134.

Huang, M.; Deng, B. W.; Zhao, X. L.; Zhang, Z. Y.; Li, F.; Li, K. L.; Cui, Z. H.; Kong, L. X.; Lu, J. M.; Dong, F. et al. Template-sacrificing synthesis of well-defined asymmetrically coordinated single-atom catalysts for highly efficient CO₂ electrocatalytic reduction. ACS Nano 2022, 16, 2110–2119.

Li, Z. J.; Wang, Z. Y.; Xi, S. B.; Zhao, X. X.; Sun, T.; Li, J.; Yu, W.; Xu, H. M.; Herng, T. S.; Hai, X. et al. Tuning the spin density of cobalt single-atom catalysts for efficient oxygen evolution. ACS Nano 2021, 15, 7105–7113.

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.

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.

Yuan, K.; Lützenkirchen-Hecht, D.; Li, L. B.; Shuai, L.; Li, Y. Z.; Cao, R.; Qiu, M.; Zhuang, X. D.; Leung, M. K. H.; Chen, Y. W. et al. Boosting oxygen reduction of single iron active sites via geometric and electronic engineering: Nitrogen and phosphorus dual coordination. J. Am. Chem. Soc. 2020, 142, 2404–2412.

Wang, J.; Li, H. G.; Liu, S. H.; Hu, Y. F.; Zhang, J.; Xia, M. R.; Hou, Y. L.; Tse, J.; Zhang, J. J.; Zhao, Y. F. Turning on Zn 4s electrons in a N₂-Zn-B₂ configuration to stimulate remarkable ORR performance. Angew. Chem., Int. Ed. 2021, 60, 181–185.

Wang, B. Q.; Cheng, C.; Jin, M. M.; He, J.; Zhang, H.; Ren, W.; Li, J.; Wang, D. S.; Li, Y. D. A site distance effect induced by reactant molecule matchup in single-atom catalysts for Fenton-like reactions. Angew. Chem., Int. Ed. 2022, 61, e202207268.

Wei, S. J.; Li, A.; Liu, J. C.; Li, Z.; Chen, W. X.; Gong, Y.; Zhang, Q. H.; Cheong, W. C.; Wang, Y.; Zheng, L. R. et al. Direct observation of noble metal nanoparticles transforming to thermally stable single atoms. Nat. Nanotechnol. 2018, 13, 856–861.

Li, S. M.; Zhao, S. Q.; Lu, X. Y.; Ceccato, M.; Hu, X. M.; Roldan, A.; Catalano, J.; Liu, M.; Skrydstrup, T.; Daasbjerg, K. Low-valence Zn^δ+ (0 < δ < 2) single-atom material as highly efficient electrocatalyst for CO₂ reduction. Angew. Chem., Int. Ed. 2021, 60, 22826–22832.

Li, Y.; Li, J. W.; Huang, J. H.; Chen, J. X.; Kong, Y.; Yang, B.; Li, Z. J.; Lei, L. C.; Chai, G. L.; Wen, Z. H. et al. Boosting electroreduction kinetics of nitrogen to ammonia via tuning electron distribution of single-atomic iron sites. Angew. Chem., Int. Ed. 2021, 60, 9078–9085.

Chen, Y. J.; Gao, R.; Ji, S. F.; Li, H. J.; Tang, K.; Jiang, P.; Hu, H. B.; Zhang, Z. D.; Hao, H. G.; Qu, Q. Y. et al. Atomic-level modulation of electronic density at cobalt single-atom sites derived from metal-organic frameworks: Enhanced oxygen reduction performance. Angew. Chem., Int. Ed. 2021, 60, 3212–3221.

Jiang, Z. L.; Wang, T.; Pei, J. J.; Shang, H. S.; Zhou, D. N.; Li, H. J.; Dong, J. C.; Wang, Y.; Cao, R.; Zhuang, Z. B. et al. Discovery of main group single Sb-N₄ active sites for CO₂ electroreduction to formate with high efficiency. Energy Environ. Sci. 2020, 13, 2856–2863.

Zhang, L.; Peisert, H.; Biswas, I.; Knupfer, M.; Batchelor, D.; Chassé, T. Growth of zinc phthalocyanine onto ZnS film investigated by synchrotron radiation-excited X-ray photoelectron and near-edge absorption spectroscopy. Surf. Sci. 2005, 596, 98–107.

Wang, Q.; Ina, T.; Chen, W. T.; Shang, L.; Sun, F. F.; Wei, S. H.; Sun-Waterhouse, D.; Telfer, S. G.; Zhang, T. R.; Waterhouse, G. I. N. Evolution of Zn(II) single atom catalyst sites during the pyrolysis-induced transformation of ZIF-8 to N-doped carbons. Sci. Bull. 2020, 65, 1743–1751.

Nørskov, J. K.; Abild-Pedersen, F.; Studt, F.; Bligaard. T. Density functional theory in surface chemistry and catalysis. Proc. Natl. Acad. Sci. USA 2011, 108, 937–943.

Medford, A. J.; Moses, P. G.; Jacobsen, K. W.; Peterson, A. A. A career in catalysis: Jens Kehlet Nørskov. ACS Catal. 2022, 12, 9679–9689.

Chen, Z. Q.; Huang, A. J.; Yu, K.; Cui, T. T.; Zhuang, Z. W.; Liu, S. J.; Li, J. Z.; Tu, R. Y.; Sun, K. A.; Tan, X. et al. Fe₁N₄-O₁ site with axial Fe-O coordination for high-selective CO₂ reduction over wide potential range. Energy Environ. Sci. 2021, 14, 3430–3437.

Liu, J. C.; Xiao, H.; Li, J. Constructing high-loading single-atom/cluster catalysts via an electrochemical potential window strategy. J. Am. Chem. Soc. 2020, 142, 3375–3383.