Screening of transition metal oxides for electrocatalytic nitrate reduction to ammonia at large currents

Zheng, J. X.; Liu, X.; Zheng, Y. G.; Gandi, A. N.; Kuai, X. X.; Wang, Z. C.; Zhu, Y. P.; Zhuang, Z. C.; Liang, H. F. Ag _x Zn _y protective coatings with selective Zn²⁺/H⁺ binding enable reversible Zn anodes. Nano Lett. 2023, 23, 6156–6163.

Kang, Q.; Zhuang, Z. C.; Liu, Y. J.; Liu, Z. H.; Li, Y.; Sun, B.; Pei, F.; Zhu, H.; Li, H. F.; Li, P. L. et al. Engineering the structural uniformity of gel polymer electrolytes via pattern-guided alignment for durable, safe solid-state lithium metal batteries. Adv. Mater. 2023, 35, 2303460.

Hu, B.; Xu, J.; Fan, Z. J.; Xu, C.; Han, S. C.; Zhang, J. X.; Ma, L. B.; Ding, B.; Zhuang, Z. C.; Kang, Q. et al. Covalent organic framework based lithium-sulfur batteries: Materials, interfaces, and solid-state electrolytes. Adv. Energy Mater. 2023, 13, 2203540.

Kang, Q.; Zhuang, Z. C.; Li, Y.; Zuo, Y. Z.; Wang, J.; Liu, Y. J.; Shi, C. Q.; Chen, J.; Li, H. F.; Jiang, P. K. et al. Manipulating dielectric property of polymer coatings toward high-retention-rate lithium metal full batteries under harsh critical conditions. Nano Res. 2023, 16, 9240–9249.

Kang, Q.; Li, Y.; Zhuang, Z. C.; Wang, D. S.; Zhi, C. Y.; Jiang, P. K.; Huang, X. Y. Dielectric polymer based electrolytes for high-performance all-solid-state lithium metal batteries. J. Energy Chem. 2022, 69, 194–204.

Zhang, E. H.; Hu, X.; Meng, L. Z.; Qiu, M.; Chen, J. X.; Liu, Y. J.; Liu, G. Y.; Zhuang, Z. C.; Zheng, X. B.; Zheng, L. R. et al. Single-atom yttrium engineering janus electrode for rechargeable Na-S batteries. J. Am. Chem. Soc. 2022, 144, 18995–19007.

Zhuang, Z. C.; Li, Y. H.; Yu, R. H.; Xia, L. X.; Yang, J. R.; Lang, Z. Q.; Zhu, J. X.; Huang, J. Z.; Wang, J. O.; Wang, Y. et al. Reversely trapping atoms from a perovskite surface for high-performance and durable fuel cell cathodes. Nat. Catal. 2022, 5, 300–310.

Li, X.; Guan, Q. H.; Zhuang, Z. C.; Zhang, Y. Z.; Lin, Y. H.; Wang, J.; Shen, C. Y.; Lin, H. Z.; Wang, Y. L.; Zhan, L. et al. Ordered mesoporous carbon grafted mxene catalytic heterostructure as Li-ion kinetic pump toward high-efficient sulfur/sulfide conversions for Li-S battery. ACS Nano 2023, 17, 1653–1662.

Zhang, X.; Li, X. Y.; Zhang, Y. Z.; Li, X.; Guan, Q. H.; Wang, J.; Zhuang, Z. C.; Zhuang, Q.; Cheng, X. M.; Liu, H. T. et al. Accelerated Li⁺ desolvation for diffusion booster enabling low-temperature sulfur redox kinetics via electrocatalytic carbon-grazfted-CoP porous nanosheets. Adv. Funct. Mater. 2023, 33, 2302624.

Wang, R.; Wu, Q. F.; Wu, M. J.; Zheng, J. X.; Cui, J.; Kang, Q.; Qi, Z. B.; Ma, J. D.; Wang, Z. C.; Liang, H. F. Interface engineering of Zn meal anodes using electrochemically inert Al₂O₃ protective nanocoatings. Nano Res. 2022, 15, 7227–7233.

Li, Y.; Hua, Y. Q.; Sun, N.; Liu, S. J.; Li, H. X.; Wang, C.; Yang, X. Y.; Zhuang, Z. C.; Wang, L. L. Moiré superlattice engineering of two-dimensional materials for electrocatalytic hydrogen evolution reaction. Nano Res. 2023, 16, 8712–8728.

Li, X. Y.; Zhuang, Z. C.; Chai, J.; Shao, R. W.; Wang, J. H.; Jiang, Z. L.; Zhu, S. W.; Gu, H. F.; Zhang, J.; Ma, Z. T. et al. Atomically strained metal sites for highly efficient and selective photooxidation. Nano Lett. 2023, 23, 2905–2914.

Sun, C.; Wang, L. L.; Zhao, W. W.; Xie, L. B.; Wang, J.; Li, J. M.; Li, B. X.; Liu, S. J.; Zhuang, Z. C.; Zhao, Q. Atomic-level design of active site on two-dimensional MoS₂ toward efficient hydrogen evolution: Experiment, theory, and artificial intelligence modelling. Adv. Funct. Mater. 2022, 32, 2206163.

Huang, J. Z.; Zhuang, Z. C.; Zhao, Y.; Chen, J. Q.; Zhuo, Z. W.; Liu, Y. W.; Lu, N.; Li, H. Q.; Zhai, T. Y. Back-gated van der waals heterojunction manipulates local charges toward fine-tuning hydrogen evolution. Angew. Chem. 2022, 134, e202203522.

Hao, J. C.; Zhuang, Z. C.; Hao, J. C.; Wang, C.; Lu, S. L.; Duan, F.; Xu, F. P.; Du, M. L.; Zhu, H. Interatomic electronegativity offset dictates selectivity when catalyzing the CO₂ reduction reaction. Adv. Energy Mater. 2022, 12, 2200579.

Zhuang, Z. C.; Xia, L. X.; Huang, J. Z.; Zhu, P.; Li, Y.; Ye, C. L.; Xia, M. G.; Yu, R. H.; Lang, Z. Q.; Zhu, J. X. et al. Continuous modulation of electrocatalytic oxygen reduction activities of single-atom catalysts through p-n junction rectification. Angew. Chem., Int. Ed. 2023, 62, e202212335.

Sharma, R.; Sharma, A.; Agarwal, S.; Dhaka, M. S. Stability and efficiency issues, solutions and advancements in perovskite solar cells: A review. Solar Energy 2022, 244, 516–535.

Qi, Z. B.; Zeng, Y.; Hou, Z.; Zhu, W. J.; Wei, B. B.; Yang, Y.; Lin, B. L.; Liang, H. F. Heterointerface engineering of Ni/Ni₃N hierarchical nanoarrays for efficient alkaline hydrogen evolution. Nano Res. 2023, 16, 4803–4811.

Mei, G.; Liang, H. F.; Wei, B. B.; Shi, H. H.; Ming, F. W.; Xu, X.; Wang, Z. C. Bimetallic MnCo selenide yolk shell structures for efficient overall water splitting. Electrochim. Acta 2018, 290, 82–89.

Zhu, W. J.; Yao, F.; Cheng, K. J.; Zhao, M. T.; Yang, C. J.; Dong, C. L.; Hong, Q. M.; Jiang, Q.; Wang, Z. C.; Liang, H. F. Direct dioxygen radical coupling driven by octahedral ruthenium-oxygen-cobalt collaborative coordination for acidic oxygen evolution reaction. J. Am. Chem. Soc. 2023, 145, 17995–18006.

Liang, H. F.; Cao, Z.; Xia, C.; Ming, F. W.; Zhang, W. L.; Emwas, A. H.; Cavallo, L.; Alshareef, H. N. Tungsten blue oxide as a reusable electrocatalyst for acidic water oxidation by plasma-induced vacancy engineering. CCS Chem. 2021, 3, 1553–1561.

Zhu, W. J.; Zhang, X. Y.; Yao, F.; Huang, R. P.; Chen, Y.; Chen, C. L.; Fei, J. W.; Chen, Y. Q.; Wang, Z. C.; Liang, H. F. A hydrazine-nitrate flow battery catalyzed by a bimetallic RuCo precatalyst for wastewater purification along with simultaneous generation of ammonia and electricity. Angew. Chem. 2023, 135, e202300390.

Zhu, W. J.; Yao, F.; Wu, Q. F.; Jiang, Q.; Wang, J. X.; Wang, Z. C.; Liang, H. F. Weakened d-p orbital hybridization in situ reconstructed Ru/β-Co(OH)₂ heterointerfaces for accelerated ammonia electrosynthesis from nitrates. Energy Environ. Sci. 2023, 16, 2483–2493.

Smith, C.; Hill, A. K.; Torrente-Murciano, L. Current and future role of Haber–Bosch ammonia in a carbon-free energy landscape. Energy Environ. Sci. 2020, 13, 331–344.

MacFarlane, D. R.; Cherepanov, P. V.; Choi, J.; Suryanto, B. H. R.; Hodgetts, R. Y.; Bakker, J. M.; Ferrero Vallana, F. M.; Simonov, A. N. A roadmap to the ammonia economy. Joule 2020, 4, 1186–1205.

Foster, S. L.; Bakovic, S. I. P.; Duda, R. D.; Maheshwari, S.; Milton, R. D.; Minteer, S. D.; Janik, M. J.; Renner, J. N.; Greenlee, L. F. Catalysts for nitrogen reduction to ammonia. Nat. Catal. 2018, 1, 490–500.

Xu, H.; Ma, Y. Y.; Chen, J.; Zhang, W. X.; Yang, J. P. Electrocatalytic reduction of nitrate-a step towards a sustainable nitrogen cycle. Chem. Soc. Rev. 2022, 51, 2710–2758.

Wang, Y. T.; Wang, C. H.; Li, M. Y.; Yu, Y. F.; Zhang, B. Nitrate electroreduction: Mechanism insight, in situ characterization, performance evaluation, and challenges. Chem. Soc. Rev. 2021, 50, 6720–6733.

Singh, N.; Goldsmith, B. R. Role of electrocatalysis in the remediation of water pollutants. ACS Catal. 2020, 10, 3365–3371.

Chen, G. F.; Yuan, Y. F.; Jiang, H. F.; Ren, S. Y.; Ding, L. X.; Ma, L.; Wu, T. P.; Lu, J.; Wang, H. H. Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper-molecular solid catalyst. Nat. Energy 2020, 5, 605–613.

Zhu, H.; Sun, S. H.; Hao, J. C.; Zhuang, Z. C.; Zhang, S. G.; Wang, T. D.; Kang, Q.; Lu, S. L.; Wang, X. F.; Lai, F. L. et al. A high-entropy atomic environment converts inactive to active sites for electrocatalysis. Energy Environ. Sci. 2023, 16, 619–628.

Hao, J. C.; Zhuang, Z. C.; Cao, K. C.; Gao, G. H.; Wang, C.; Lai, F. L.; Lu, S. L.; Ma, P. M.; Dong, W. F.; Liu, T. X. et al. Unraveling the electronegativity-dominated intermediate adsorption on high-entropy alloy electrocatalysts. Nat. Commun. 2022, 13, 2662.

Hao, J. C.; Zhu, H.; Zhuang, Z. C.; Zhao, Q.; Yu, R. H.; Hao, J. C.; Kang, Q.; Lu, S. L.; Wang, X. F.; Wu, J. S. et al. Competitive trapping of single atoms onto a metal carbide surface. ACS Nano 2023, 17, 6955–6965.

Liu, Z. H.; Du, Y.; Yu, R. H.; Zheng, M. B.; Hu, R.; Wu, J. S.; Xia, Y. Y.; Zhuang, Z. C.; Wang, D. S. Tuning mass transport in electrocatalysis down to sub-5 nm through nanoscale grade separation. Angew. Chem., Int. Ed. 2023, 62, e202212653.

Hao, J. C.; Zhuang, Z. C.; Hao, J. C.; Cao, K. C.; Hu, Y. X.; Wu, W. B.; Lu, S. L.; Wang, C.; Zhang, N.; Wang, D. S. et al. Strain relaxation in metal alloy catalysts steers the product selectivity of electrocatalytic CO₂ reduction. ACS Nano 2022, 16, 3251–3263.

Niu, H.; Zhang, Z. F.; Wang, X. T.; Wan, X. H.; Shao, C.; Guo, Y. Z. Theoretical insights into the mechanism of selective nitrate-to-ammonia electroreduction on single-atom catalysts. Adv. Funct. Mater. 2020, 31, 2008533.

Wang, Y. Y.; Wu, D. H.; Lv, P.; He, B. L.; Li, X.; Ma, D. W.; Jia, Y. Theoretical insights into the electroreduction of nitrate to ammonia on graphene-based single-atom catalysts. Nanoscale 2022, 14, 10862–10872.

Wang, Y. T.; Zhou, W.; Jia, R. R.; Yu, Y. F.; Zhang, B. Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia. Angew. Chem., Int. Ed. 2020, 59, 5350–5354.

Zhang, S.; Li, M.; Li, J. C.; Song, Q. N.; Liu, X. High-ammonia selective metal-organic framework-derived co-doped Fe/Fe₂O₃ catalysts for electrochemical nitrate reduction. Proc. Natl. Acad. Sci. USA 2022, 119, e2115504119.

Zhang, R.; Guo, Y.; Zhang, S. C.; Chen, D.; Zhao, Y. W.; Huang, Z. D.; Ma, L. T.; Li, P.; Yang, Q.; Liang, G. J. et al. Efficient ammonia electrosynthesis and energy conversion through a Zn-nitrate battery by iron doping engineered nickel phosphide catalyst. Adv. Energy Mater. 2022, 12, 2103872.

Wu, Z. Y.; Karamad, M.; Yong, X.; Huang, Q. Z.; Cullen, D. A.; Zhu, P.; Xia, C.; Xiao, Q. F.; Shakouri, M.; Chen, F. Y. et al. Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst. Nat. Commun. 2021, 12, 2870.

Li, P. P.; Jin, Z. Y.; Fang, Z. W.; Yu, G. H. A single-site iron catalyst with preoccupied active centers that achieves selective ammonia electrosynthesis from nitrate. Energy Environ. Sci. 2021, 14, 3522–3531.

Fan, X. Y.; Xie, L. S.; Liang, J.; Ren, Y. C.; Zhang, L. C.; Yue, L. C.; Li, T. S.; Luo, Y. L.; Li, N.; Tang, B. et al. In situ grown Fe₃O₄ particle on stainless steel: A highly efficient electrocatalyst for nitrate reduction to ammonia. Nano Res. 2022, 15, 3050–3055

Fu, X. B.; Zhao, X. G.; Hu, X. B.; He, K.; Yu, Y. N.; Li, T.; Tu, Q.; Qian, X.; Yue, Q.; Wasielewski, M. R. et al. Alternative route for electrochemical ammonia synthesis by reduction of nitrate on copper nanosheets. Appl. Mater. Today 2020, 19, 100620.

Hu, Q.; Qin, Y. J.; Wang, X. D.; Wang, Z. Y.; Huang, X. W.; Zheng, H. J.; Gao, K. R.; Yang, H. P.; Zhang, P. X.; Shao, M. H. et al. Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate-ammonia conversion. Energy Environ. Sci. 2021, 14, 4989–4997.

Wang, J.; Cai, C.; Wang, Y. A.; Yang, X. M.; Wu, D. J.; Zhu, Y. M.; Li, M. H.; Gu, M.; Shao, M. H. Electrocatalytic reduction of nitrate to ammonia on low-cost ultrathin CoO _x nanosheets. ACS Catal. 2021, 11, 15135–15140.

Deng, Z. Q.; Liang, J.; Liu, Q.; Ma, C. Q.; Xie, L. S.; Yue, L. C.; Ren, Y. C.; Li, T. S.; Luo, Y. S.; Li, N. et al. High-efficiency ammonia electrosynthesis on self-supported Co₂AlO₄ nanoarray in neutral media by selective reduction of nitrate. Chem. Eng. J. 2022, 435, 135104.

Liu, S. S.; Qian, T.; Wang, M. F.; Ji, H. Q.; Shen, X. W.; Wang, C.; Yan, C. L. Proton-filtering covalent organic frameworks with superior nitrogen penetration flux promote ambient ammonia synthesis. Nat. Catal. 2021, 4, 322–331.

Liu, P. Y.; Shi, K.; Chen, W. Z.; Gao, R.; Liu, Z. L.; Hao, H. G.; Wang, Y. Q. Enhanced electrocatalytic nitrogen reduction reaction performance by interfacial engineering of MOF-based sulfides FeNi₂S₄/NiS hetero-interface. Appl. Catal. B Environ. 2021, 287, 119956.

Hao, Y. C.; Guo, Y.; Chen, L. W.; Shu, M.; Wang, X. Y.; Bu, T. A.; Gao, W. Y.; Zhang, N.; Su, X.; Feng, X. et al. Promoting nitrogen electroreduction to ammonia with bismuth nanocrystals and potassium cations in water. Nat. Catal. 2019, 2, 448–456.

Liu, R. Q.; Guo, T.; Fei, H.; Wu, Z. Z.; Wang, D. Z.; Liu, F. Y. Highly efficient electrocatalytic N₂ reduction to ammonia over metallic 1T phase of MoS₂ enabled by active sites separation mechanism. Adv. Sci. 2022, 9, 2103583.

Wen, Y. K.; Zhu, H.; Hao, J. C.; Lu, S. L.; Zong, W.; Lai, F. L.; Ma, P. M.; Dong, W. F.; Liu, T. X.; Du, M. L. Metal-free boron and sulphur co-doped carbon nanofibers with optimized p-band centers for highly efficient nitrogen electroreduction to ammonia. Appl. Catal. B Environ. 2021, 292, 120144.

Geng, Z. G.; Liu, Y.; Kong, X. D.; Li, P.; Li, K.; Liu, Z. Y.; Du, J. J.; Shu, M.; Si, R.; Zeng, J. Achieving a record-high yield rate of 120.9 ${\text{µg}}_{{\mathrm{N}\mathrm{H}}_3}\cdot {{\mathrm{m}\mathrm{g}}_{\mathrm{c}\mathrm{a}\mathrm{t}.}}^{-1}\cdot {\mathrm{h}}^{-1}$ for N₂ electrochemical reduction over Ru single-atom catalysts. Adv. Mater. 2018, 30, 1803498.

Wang, H. J.; Yu, H. J.; Wang, Z. Q.; Li, Y. H.; Xu, Y.; Li, X. N.; Xue, H. R.; Wang, L. Electrochemical fabrication of porous Au film on Ni foam for nitrogen reduction to ammonia. Small 2019, 15, 1804769.

Zhang, J.; Ji, Y. J.; Wang, P. T.; Shao, Q.; Li, Y. Y.; Huang, X. Q. Adsorbing and activating N₂ on heterogeneous Au-Fe₃O₄ nanoparticles for N₂ fixation. Adv. Funct. Mater. 2020, 30, 1906579.

Jin, M.; Zhang, X.; Han, M. M.; Wang, H. J.; Wang, G. Z.; Zhang, H. M. Efficient electrochemical N₂ fixation by doped-oxygen-induced phosphorus vacancy defects on copper phosphide nanosheets. J. Mater. Chem. A 2020, 8, 5936–5942.

Zhu, T. H.; Chen, Q. S.; Liao, P.; Duan, W. J.; Liang, S.; Yan, Z.; Feng, C. H. Single-atom Cu catalysts for enhanced electrocatalytic nitrate reduction with significant alleviation of nitrite production. Small 2020, 16, 2004526.

Liu, H. Z.; Park, J.; Chen, Y. F.; Qiu, Y.; Cheng, Y.; Srivastava, K.; Gu, S.; Shanks, B. H.; Roling, L. T.; Li, W. Z. Electrocatalytic nitrate reduction on oxide-derived silver with tunable selectivity to nitrite and ammonia. ACS Catal. 2021, 11, 8431–8442.

Chen, F. Y.; Wu, Z. Y.; Gupta, S.; Rivera, D. J.; Lambeets, S. V.; Pecaut, S.; Kim, J. Y. T.; Zhu, P.; Finfrock, Y. Z.; Meira, D. M. et al. Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst. Nat. Nanotechnol. 2022, 17, 759–767.

Fang, J. Y.; Zheng, Q. Z.; Lou, Y. Y.; Zhao, K. M.; Hu, S. N.; Li, G.; Akdim, O.; Huang, X. Y.; Sun, S. G. Ampere-level current density ammonia electrochemical synthesis using CuCo nanosheets simulating nitrite reductase bifunctional nature. Nat. Commun. 2022, 13, 7899.

Wang, Y. H.; Xu, A. N.; Wang, Z. Y.; Huang, L. S.; Li, J.; Li, F. W.; Wicks, J.; Luo, M. C.; Nam, D. H.; Tan, C. S. et al. Enhanced nitrate-to-ammonia activity on copper-nickel alloys via tuning of intermediate adsorption. J. Am. Chem. Soc. 2020, 142, 5702–5708.

Xiao, L.; Dai, W. D.; Mou, S. Y.; Wang, X. Y.; Cheng, Q.; Dong, F. Coupling electrocatalytic cathodic nitrate reduction with anodic formaldehyde oxidation at ultra-low potential over Cu₂O. Energy Environ. Sci. 2023, 16, 2696–2704.

Biesinger, M. C.; Payne, B. P.; Grosvenor, A. P.; Lau, L. W. M.; Gerson, A. R.; Smart, R. S. C. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl. Surf. Sci. 2011, 257, 2717–2730.

Jia, R. R.; Wang, Y. T.; Wang, C. H.; Ling, Y. F.; Yu, Y. F.; Zhang, B. Boosting selective nitrate electroreduction to ammonium by constructing oxygen vacancies in TiO₂. ACS Catal. 2020, 10, 3533–3540.

Wang, Y. T.; Li, H. J.; Zhou, W.; Zhang, X.; Zhang, B.; Yu, Y. F. Structurally disordered RuO₂ nanosheets with rich oxygen vacancies for enhanced nitrate electroreduction to ammonia. Angew. Chem., Int. Ed. 2022, 61, e202202604.

Gao, J. N.; Jiang, B.; Ni, C. C.; Qi, Y. F.; Zhang, Y. Q.; Oturan, N.; Oturan, M. A. Non-precious Co₃O₄-TiO₂/Ti cathode based electrocatalytic nitrate reduction: Preparation, performance and mechanism. Appl. Catal. B Environ. 2019, 254, 391–402.