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Screening MXene-based single-atom catalysts for selective nitrate-to-ammonia electroreduction

筛选电催化硝酸根还原制氨的MXene基单原子催化剂

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Abstract

Electrocatalytic nitrate reduction to ammonia (NRA) is a promising way to regulate the global nitrogen cycle and synthesize ammonia. The key factor to achieve efficient NRA is to develop desired catalysts with high activity, selectivity and stability. Herein, a new family of single-atom catalysts (SACs) for NRA are screened by anchoring transition metal (TM: 3d = Sc-Zn, 4d = Y-Cd, 5d = La-Hg) atoms on two-dimensional Ti3C2O2 MXene (Ti3C2O2-TM). Using density functional theory calculations, the surface O functional group on Ti3C2O2 is found to deliver high anchoring ability for TM, resulting in excellent anti-dissolution stability. Besides, strong p-d coupling between the anchored TM and the nitrate facilitates nitrate activation. Ten Ti3C2O2-TMs with orbitals around d5 (TM = Cr, Mn, Fe, Tc, Ru, W, Re, Os, Ir, and Pt) are first screened out based on the relatively high unsaturated anchored TM d orbitals at Fermi level to achieve good stability and nitrate activation. The most favorable reaction pathway is determined being the continuous deoxygenation, followed by hydrogenation: NO −3 → *NO3 → *NO2 → *NO → *N → *NH → *NH2 → *NH3 → NH3(g). Three Ti3C2O2-TMs including Ti3C2O2-CrSA, Ti3C2O2-ReSA, and Ti3C2O2-OsSA with low overpotentials are regarded as the outstanding catalysts for NRA. These findings could open up new strategies for an advanced ammonia synthesis route with low energy consumption and low carbon emission.

摘要

电催化硝酸根还原制氨是调节全球氮循环和合成氨的一种很有前景的方法. 当前实现高效硝酸根还原制氨(NRA)的关键问题是开发具有高活性、 选择性和稳定性的催化剂. 本文通过把过渡金属(TM: 3d = Sc-Zn, 4d = Y-Cd, 5d = La-Hg)锚定在二维材料Ti3C2O2 MXene (Ti3C2O2-TM)上, 筛选出新的NRA单原子催化剂. 本工作采用密度泛函 理论进行理论计算, 发现Ti3C2O2上的表面O官能团对TM具有较高的锚 定能力, 同时材料拥有良好的抗溶解稳定性. 此外, 锚定的TM与硝酸根之间强的p-d耦合作用使NO3−易于活化. 锚定TM在费米能级处有较高的不饱和d轨道, 具有良好的稳定性和NO3−活化能力. 基于此, 本文筛选出10种前线分子轨道在d5附近的Ti3C2O2-TMs (TM = Cr, Mn, Fe, Tc, Ru, W, Re, Os, Ir, Pt), 并且最有利的反应路径是持续的脱氧加氢: NO −3 − → *NO3 → *NO2 → *NO → *N → *NH → *NH2 → *NH3 → NH3(g). 本 工作认为Ti3C2O2-CrSA、 Ti3C2O2-ReSA和Ti3C2O2-OsSA这3种具有低NRA 过电位的Ti3C2O2-TM是优异的NRA催化剂. 这些发现为设计低能耗、 低碳排放的先进氨合成路线提供了新策略.

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References

  1. Wu ZY, Karamad M, Yong X, et al. Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst. Nat Commun, 2021, 12: 2870

    CAS  Google Scholar 

  2. Fu X, Zhao X, Hu X, et al. Alternative route for electrochemical ammonia synthesis by reduction of nitrate on copper nanosheets. Appl Mater Today, 2020, 19: 100620

    Google Scholar 

  3. Xu H, Wu J, Luo W, et al. Dendritic cell-inspired designed architectures toward highly efficient electrocatalysts for nitrate reduction reaction. Small, 2020, 16: 2001775

    CAS  Google Scholar 

  4. Liu H, Park J, Chen Y, et al. Electrocatalytic nitrate reduction on oxide-derived silver with tunable selectivity to nitrite and ammonia. ACS Catal, 2021, 11: 8431–8442

    CAS  Google Scholar 

  5. Walls JM, Sagu JS, Upul Wijayantha KG. Microwave synthesised Pd-TiO2 for photocatalytic ammonia production. RSC Adv, 2019, 9: 6387–6394

    CAS  Google Scholar 

  6. Shi MM, Bao D, Li SJ, et al. Anchoring PdCu amorphous nanocluster on graphene for electrochemical reduction of N2 to NH3 under ambient conditions in aqueous solution. Adv Energy Mater, 2018, 8: 1800124

    Google Scholar 

  7. Liu HM, Han SH, Zhao Y, et al. Surfactant-free atomically ultrathin rhodium nanosheet nanoassemblies for efficient nitrogen electro-reduction. J Mater Chem A, 2018, 6: 3211–3217

    CAS  Google Scholar 

  8. Liu JX, Richards D, Singh N, et al. Activity and selectivity trends in electrocatalytic nitrate reduction on transition metals. ACS Catal, 2019, 9: 7052–7064

    CAS  Google Scholar 

  9. Chen ZW, Yan J, Jiang Q. Single or double: Which is the altar of atomic catalysts for nitrogen reduction reaction? Small Methods, 2019, 3: 1800291

    Google Scholar 

  10. Wang S, Shi L, Bai X, et al. Highly efficient photo-/electrocatalytic reduction of nitrogen into ammonia by dual-metal sites. ACS Cent Sci, 2020, 6: 1762–1771

    CAS  Google Scholar 

  11. Wei L, Liu DJ, Rosales BA, et al. Mild and selective hydrogenation of nitrate to ammonia in the absence of noble metals. ACS Catal, 2020, 10: 3618–3628

    CAS  Google Scholar 

  12. Wang Z, Zheng K, Liu S, et al. Electrocatalytic nitrogen reduction to ammonia by Fe2O3 nanorod array on carbon cloth. ACS Sustain Chem Eng, 2019, 7: 11754–11759

    CAS  Google Scholar 

  13. Chen S, Bu M, Zhou Z, et al. Boosting nitrogen reduction to ammonia on Fe-N3S sites by introduction S into defect graphene. Mater Today Energy, 2022, 25: 100954

    CAS  Google Scholar 

  14. Li Z, Deng Z, Ouyang L, et al. CeO2 nanoparticles with oxygen vacancies decorated N-doped carbon nanorods: A highly efficient catalyst for nitrate electroreduction to ammonia. Nano Res, 2022, 15: 8914–8921

    CAS  Google Scholar 

  15. Li LX, Sun WJ, Zhang HY, et al. Highly efficient and selective nitrate electroreduction to ammonia catalyzed by molecular copper catalyst@Ti3C2Tx MXene. J Mater Chem A, 2021, 9: 21771–21778

    CAS  Google Scholar 

  16. Lu X, Song H, Cai J, et al. Recent development of electrochemical nitrate reduction to ammonia: A mini review. Electrochem Commun, 2021, 129: 107094

    CAS  Google Scholar 

  17. Hu T, Yang J, Li W, et al. Quantifying the rigidity of 2D carbides (MXenes). Phys Chem Chem Phys, 2020, 22: 2115–2121

    CAS  Google Scholar 

  18. Zhang J, Zhao Y, Guo X, et al. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction. Nat Catal, 2018, 1: 985–992

    CAS  Google Scholar 

  19. Gao G, O’Mullane AP, Du A. 2D MXenes: A new family of promising catalysts for the hydrogen evolution reaction. ACS Catal, 2017, 7: 494–500

    CAS  Google Scholar 

  20. Gao Y, Zhuo H, Cao Y, et al. A theoretical study of electrocatalytic ammonia synthesis on single metal atom/MXene. Chin J Catal, 2019, 40: 152–159

    CAS  Google Scholar 

  21. Cheng Y, Dai J, Song Y, et al. Single molybdenum atom anchored on 2D Ti2NO2 MXene as a promising electrocatalyst for N2 fixation. Nanoscale, 2019, 11: 18132–18141

    CAS  Google Scholar 

  22. Zhang M, Yin H, Jin F, et al. Vacancy engineering of oxidized Nb2CTx MXenes for a biased nitrogen fixation. Green Energy Environ, 2022, doi: https://doi.org/10.1016/j.gee.2022.01.010

  23. Ling C, Shi L, Ouyang Y, et al. Nanosheet supported single-metal atom bifunctional catalyst for overall water splitting. Nano Lett, 2017, 17: 5133–5139

    CAS  Google Scholar 

  24. Zhao Q, Zhang C, Hu R, et al. Selective etching quaternary MAX phase toward single atom copper immobilized MXene (Ti3C2Clx) for efficient CO2 electroreduction to methanol. ACS Nano, 2021, 15: 4927–4936

    CAS  Google Scholar 

  25. Li N, Wang X, Lu X, et al. Comprehensive mechanism of CO2 electroreduction on non-noble metal single-atom catalysts of Mo2CS2-MXene. Chem Eur J, 2021, 27: 17900–17909

    CAS  Google Scholar 

  26. Kuznetsov DA, Chen Z, Abdala PM, et al. Single-atom-substituted Mo2CTx:Fe-layered carbide for selective oxygen reduction to hydrogen peroxide: Tracking the evolution of the MXene phase. J Am Chem Soc, 2021, 143: 5771–5778

    CAS  Google Scholar 

  27. Hu T, Wang M, Guo C, et al. Functionalized MXenes for efficient electrocatalytic nitrate reduction to ammonia. J Mater Chem A, 2022, 10: 8923–8931

    CAS  Google Scholar 

  28. Wang Y, Wang C, Li M, et al. Nitrate electroreduction: Mechanism insight, in situ characterization, performance evaluation, and challenges. Chem Soc Rev, 2021, 50: 6720–6733

    CAS  Google Scholar 

  29. Hajiyani H, Pentcheva R. Surface termination and composition control of activity of the CoxNi1−xFe2O4(001) surface for water oxidation: Insights from DFT + U calculations. ACS Catal, 2018, 8: 11773–11782

    CAS  Google Scholar 

  30. Bae S, Kang YG, Khazaei M, et al. Electronic and magnetic properties of carbide MXenes—The role of electron correlations. Mater Today Adv, 2021, 9: 100118

    CAS  Google Scholar 

  31. 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

    CAS  Google Scholar 

  32. Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77: 3865–3868

    CAS  Google Scholar 

  33. Blöchl PE. Projector augmented-wave method. Phys Rev B, 1994, 50: 17953–17979

    Google Scholar 

  34. Hu T, Wang M, Wang X, et al. Unraveling surface functionalization of Cr2B2T2 (T = OH, O, Cl, H) MBene by first-principles calculations. Comput Mater Sci, 2021, 199: 110810

    CAS  Google Scholar 

  35. Mathew K, Sundararaman R, Letchworth-Weaver K, et al. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J Chem Phys, 2014, 140: 084106

    Google Scholar 

  36. Grimme S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem, 2006, 27: 1787–1799

    CAS  Google Scholar 

  37. Tang W, Sanville E, Henkelman G. A grid-based Bader analysis algorithm without lattice bias. J Phys-Condens Matter, 2009, 21: 084204

    CAS  Google Scholar 

  38. Wang V, Xu N, Liu JC, et al. VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code. Comput Phys Commun, 2021, 267: 108033

    CAS  Google Scholar 

  39. Henkelman G, Uberuaga BP, Jónsson H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J Chem Phys, 2000, 113: 9901–9904

    CAS  Google Scholar 

  40. Greeley J, Nørskov JK. Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations. Electrochim Acta, 2007, 52: 5829–5836

    CAS  Google Scholar 

  41. Valdés Á, Qu ZW, Kroes GJ, et al. Oxidation and photo-oxidation of water on TiO2 surface. J Phys Chem C, 2008, 112: 9872–9879

    Google Scholar 

  42. Nørskov JK, Rossmeisl J, Logadottir A, et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J Phys Chem B, 2004, 108: 17886–17892

    Google Scholar 

  43. Lim J, Liu CY, Park J, et al. Structure sensitivity of Pd facets for enhanced electrochemical nitrate reduction to ammonia. ACS Catal, 2021, 11: 7568–7577

    CAS  Google Scholar 

  44. Li L, Wang X, Guo H, et al. Theoretical screening of single transition metal atoms embedded in MXene defects as superior electrocatalyst of nitrogen reduction reaction. Small Methods, 2019, 3: 1900337

    CAS  Google Scholar 

  45. Guo X, Gu J, Lin S, et al. Tackling the activity and selectivity challenges of electrocatalysts toward the nitrogen reduction reaction via atomically dispersed biatom catalysts. J Am Chem Soc, 2020, 142: 5709–5721

    CAS  Google Scholar 

  46. Wang T, Liu H, Dong A, et al. Exploration of single Fe atom supported on anatase TiO2(001) for methane oxidation: A DFT study. Chem-PhysMater, 2023, 2: 90–96

    Google Scholar 

  47. Feng Z, Tang Y, Chen W, et al. Graphdiyne coordinated transition metals as single-atom catalysts for nitrogen fixation. Phys Chem Chem Phys, 2020, 22: 9216–9224

    CAS  Google Scholar 

  48. Liu S, Liu J. Rational design of highly efficient electrocatalytic singleatom catalysts for nitrogen reduction on nitrogen-doped graphene and g-C2N supports. J Power Sources, 2022, 535: 231449

    CAS  Google Scholar 

  49. Zheng C, Zhang X, Zhou Z, et al. A first-principles study on the electrochemical reaction activity of 3d transition metal single-atom catalysts in nitrogen-doped graphene: Trends and hints. eScience, 2022, 2: 219–226

    Google Scholar 

  50. Zhao L, Han X, Kong W, et al. Graphene supported single metal atom catalysts for the efficient hydrogen oxidation reaction in alkaline media. Catal Sci Technol, 2022, 12: 530–541

    CAS  Google Scholar 

  51. Hu T, Wang C, Wang M, et al. Theoretical insights into superior nitrate reduction to ammonia performance of copper catalysts. ACS Catal, 2021, 11: 14417–14427

    CAS  Google Scholar 

  52. Li Y, Ma J, Waite TD, et al. Development of a mechanically flexible 2D-MXene membrane cathode for selective electrochemical reduction of nitrate to N2: Mechanisms and implications. Environ Sci Technol, 2021, 55: 10695–10703

    CAS  Google Scholar 

  53. Xin H, Vojvodic A, Voss J, et al. Effects of d-band shape on the surface reactivity of transition-metal alloys. Phys Rev B, 2014, 89: 115114

    Google Scholar 

  54. Ying Y, Luo X, Qiao J, et al. “More is different:” Synergistic effect and structural engineering in double-atom catalysts. Adv Funct Mater, 2021, 31: 2007423

    CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (51902218, 21972102, 22101197, and 22202144), Jiangsu Provincial Graduate Scientific Research and Practice Innovation Plan Project (KYCX21_3016), and the National Key Research and Development Program of China (2021YFA0910403). This work was also funded by the innovation platform for Academicians of Hainan Province and Suzhou Foreign Academician Workstation. We are grateful to the National Supercomputer Center in Guangzhou for the use of the high-performance computing facility.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Institute of Materials Science and Devices, School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China

    Mengting Wang  (王梦婷), Tao Hu  (胡涛), Changhong Wang  (汪昌红), Feng Du  (杜沣), Hongbin Yang  (杨鸿斌), Chunxian Guo  (郭春显) & Chang Ming Li  (李长明)

  2. College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou, 571158, China

    Wei Sun  (孙伟)

  3. Institute for Cross-field Science and College of Life Science, Qingdao University, Qingdao, 200671, China

    Chang Ming Li  (李长明)

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  1. Mengting Wang  (王梦婷)
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Contributions

Author contributions Wang M and Hu T performed the calculations and co-wrote the manuscript. Li CM and Guo C conceived the project and idea. Yang H and Sun W revised the draft before submission. All authors discussed the results and contributed to the editing of the manuscript.

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Correspondence to Chunxian Guo  (郭春显) or Chang Ming Li  (李长明).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Calculation details and supporting data are available in the online version of the paper.

Mengting Wang is a postgraduate candidate at the School of Materials Science and Engineering, Suzhou University of Science and Technology, under the supervision of Prof. Chang Ming Li and Tao Hu. Her research focuses on the theoretical calculation and catalysis research of new low-dimensional functional materials.

Tao Hu received his PhD degree from the Institute of Metal Research, Chinese Academy of Sciences in 2018. He is currently an associate professor at the School of Materials and Engineering, Suzhou University of Science and Technology. His research focuses on theoretical modeling of advanced materials.

Chunxian Guo works as a professor and executive vice chair of the School of Materials Science and Engineering, Suzhou University of Science and Technology. He obtained his PhD degree from the School of Chemical & Biomedical Engineering, Nanyang Technological University (Singapore), and then conducted training at the National University of Singapore, Case Western Reserve University, and The University of Adelaide. His research focuses on surface and interface engineering of functional nanomaterials for efficient electrocatalysis and analysis.

Chang Ming Li is currently a professor, chair of the School of Materials and Engineering at Suzhou University of Science and Technology. He received a PhD degree from Wuhan University. He worked at Motorola as a Member of Science Advisory board and Distinguish Tech Staff, at Nanyang Technical University as a full professor, as well as the dean of Materials and Energy of Southwest University and the director of the Chongqing Key Lab for Advanced Materials and Energy.

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Wang, M., Hu, T., Wang, C. et al. Screening MXene-based single-atom catalysts for selective nitrate-to-ammonia electroreduction. Sci. China Mater. 66, 2750–2758 (2023). https://doi.org/10.1007/s40843-022-2406-5

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