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Photocatalytic nitrogen fixation under an ambient atmosphere using a porous coordination polymer with bridging dinitrogen anions

Nature Chemistry volume 15, pages 286–293 (2023)Cite this article

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Abstract

The design of highly electron-active and stable heterogeneous catalysts for the ambient nitrogen reduction reaction is challenging due to the inertness of the N2 molecule. Here, we report the synthesis of a zinc-based coordination polymer that features bridging dinitrogen anionic ligands, {[Zn(L)(N2)0.5(TCNQ–TCNQ)0.5]·(TCNQ)0.5}n (L is tetra(isoquinolin-6-yl)tetrathiafulvalene and TCNQ is tetracyanoquinodimethane), and show that it is an efficient photocatalyst for nitrogen fixation under an ambient atmosphere. It exhibits an ammonia conversion rate of 140 μmol g−1 h−1 and functions well also with unpurified air as the feeding gas. Experimental and theoretical studies show that the active [Zn2+–(N≡N)−–Zn2+] sites can promote the formation of NH3 and the detachment of the NH3 formed creates unsaturated [Zn2+···Zn+] intermediates, which in turn can be refilled by external N2 sequestration and fast intermolecular electron migration. The [Zn2+···Zn+] intermediates stabilized by the sandwiched cage-like donor–acceptor–donor framework can sustain continuous catalytic cycles. This work presents an example of a molecular active site embedded within a coordination polymer for nitrogen fixation under mild conditions.

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Fig. 1: Single crystal structure of NJUZ-1.
Fig. 2: Spectroscopy characterizations and spin-density distributions of NJUZ-1.
Fig. 3: Absorption characterizations and NRR performances of NJUZ-1.
Fig. 4: Characterizations of NJUZ-1 during and after the NRR process.
Fig. 5: Possible NRR pathways of NJUZ-1.

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Data availability

All experimental details and data supporting the findings of this study are available within the paper and its Supplementary Information. The data are also available from the corresponding authors upon reasonable request. Crystallographic data for the NJUZ-1 structure have been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC 2008863. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key Research and Development Program (2018YFA0306004 and 2017YFA0208200), the National Natural Science Foundation of China (22022505, 22033004, 21875099, 21872069 and 21631006), the Fundamental Research Funds for the Central Universities of China (020514380266, 020514380272 and 020514380274), the Scientific and Technological Innovation Special Fund for Carbon Peak and Carbon Neutrality of Jiangsu Province (BK20220008), the Nanjing International Collaboration Research Program (202201007 and 2022SX00000955) and the Suzhou Gusu Leading Talent Program of Science and Technology Innovation and Entrepreneurship in Wujiang District (ZXL2021273).

Author information

Author notes

  1. These authors contributed equally: Yan Xiong, Bang Li, Yuming Gu.

Authors and Affiliations

  1. State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Yan Xiong, Bang Li, Yuming Gu, Tong Yan, Shuhua Li, Jing-Lin Zuo, Jing Ma & Zhong Jin

  2. College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, China

    Zhigang Ni

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Contributions

Y.X., B.L. J.-L.Z. and Z.J. conceived the idea of this study and designed the experiments. Y.X. and B.L. performed the sample synthesis, material characterizations, photoelectric measurements, photocatalytic tests and data analysis. Y.G., Z.N., S.L. and J.M. performed the theoretical calculations. All the authors analysed the data and discussed the results. Y.X., B.L., J.M. Z.J. and J.-L.Z. co-wrote and revised the manuscript. Z.J. and J.-L.Z. supervised the project.

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Correspondence to Jing-Lin Zuo, Jing Ma or Zhong Jin.

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Extended data

Extended Data Fig. 1 Synthetic process and 1H-NMR analysis of L.

a Schematic synthetic process of L ligand. b 1H-NMR spectrum of CDCl3 dissolved L ligand.

Extended Data Fig. 2 Schematic structure diagram of NJUZ-1.

a (2, 4, 6) 3-nodal simplified 3D topological network of NJUZ-1. b The 2D layered structure of NJUZ-1 viewed along the b axis. c The interactions of π···π stacking and C-H···N hydrogen bonds in the cage of [(L)2(Zn2N2)4].

Extended Data Fig. 3 Spectroscopy and EPR characterizations of NJUZ-1.

a The IR spectra measured in air (black curve) and vacuum (dark cyan curve). The two split peaks at around 2100 cm−1 are attributed to the cyano groups in TCNQ. b Simulated IR spectrum of C≡N bonds in NJUZ-1 calculated by DFT at level1. c Raman spectra of 14N-NJUZ-1 and 15N-NJUZ-1. The peak at ~2005 cm−1 is dinitrogen complexes for 14N-NJUZ-1. As for 15N-NJUZ-1, the 15N≡15N stretching vibration is at ~1920 cm−1, with a small red shift (~80 cm−1) compared to that of 14N-NJUZ-1. The peaks at 2224, 2203 and 2192 cm−1 are derived from the cyano groups in TCNQ. d Simulated Raman spectrum of Zn-C≡N-Zn structure calculated by DFT at level1. The insert shows the proposed Zn-C≡N-Zn structure. e Experimental solid EPR spectrum at low temperature (93 K) compared with simulated EPR spectrum (ν = 9.4452 GHz). f Experimental solid EPR spectrum of 15N-NJUZ-1 measured at room temperature (ν = 9.8519 GHz). a.u. refers to absorbance unit.

Source data

Extended Data Fig. 4 Spin-density distributions of cluster models and PBC models.

a cluster models and b PBC models. The values of spin-populations (isovalue = 0.005) on N2 ligands are given in square brackets.

Extended Data Fig. 5 Spin-density distributions of different reaction intermediates at reaction sites (ClusterA models).

The values of spin-populations (isovalue = 0.005) on N2 ligands are given in square brackets.

Extended Data Fig. 6 Structure characterizations of NJUZ-1.

a Representative TEM image of NJUZ-1. b Typical AFM image and the corresponding height profiles of NJUZ-1. c N2 adsorption isotherm of NJUZ-1 at room temperature.

Source data

Extended Data Fig. 7 TDDFT calculations of excitation energies.

a UV-Vis spectrum and fingertip aspects of NJUZ-1. b ClusterA and ClusterB models, which were built from NJUZ-1 crystal. c The TDDFT calculated orbital energy levels of ClusterA. d The TDDFT calculated orbital energy levels of ClusterB. a.u. refers to arbitrary unit.

Extended Data Fig. 8 NRR performances and structure characterizations of NJUZ-1.

a The percentage of ammonia yield rate of NJUZ-1 with unpurified air flow compared to that with N2 flow. b Total ammonia yield of NJUZ-1 after a long-term NRR process for 25 h. c Typical gas chromatograph spectrum (measured by TCD detector) of the gas byproducts yielded during the NRR process catalyzed by NJUZ-1. d XRD patterns of NJUZ-1 before and after 3, 10 and 25 h of the NRR in comparison with the simulated XRD pattern, respectively. e and f Typical TEM image of NJUZ-1 after the NRR for 3 and 10 h, respectively. g Nitrogen adsorption-desorption isotherms of representative NJUZ-1 before and after the NRR test for 25 h. a.u. refers to arbitrary unit.

Source data

Extended Data Fig. 9 Isotope labelling experiments and spin-density distributions with water in ClusterA.

a 1H NMR spectrum of the products measured from 15N-NJUZ-1 after the NRR process for 20 h under Ar atmosphere. b 2H and 1H-NMR analyses of ND3 product after the NRR process of NJUZ-1 in D2O. c Spin-density distributions in ClusterA models with H2O adsorption. The values of spin-populations (isovalue = 0.005) on N2 ligands are given in square brackets. d Solid-state NMR analyses of standard 15NH4Cl sample (black curve) and the NJUZ-1 photocatalyst after the NRR process with 15N2 feeding gas for 20 h (dark cyan curve).

Extended Data Fig. 10 Schematic crystal structure and proposed NRR reaction pathways over NJUZ-1.

a Schematic crystal structure of NJUZ-1. The purple, grey, blue, yellow, and white balls are corresponding to Zn, C, N, S, and H atoms, respectively. b Gibbs free energy profile of the NRR process over NJUZ-1 with alternating (blue), mixed (green) and distal (grey) pathways. c Proposed reaction pathways for the NRR process over NJUZ-1. d Charge variation of the N2-mHn species along the possible alternating, mixed and distal pathways, respectively.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–7 and Supplementary Tables 1–10.

Supplementary Data

Crystallographic data for NJUZ-1, CCDC 2008863.

Source data

Source Data Fig. 2a

Simulated Raman spectra data of Zn–N2–Zn structure.

Source Data Fig. 2b

Raman spectra data of 14N-NJUZ-1 and 15N-NJUZ-1.

Source Data Fig. 2c

EPR spectrum data of NJUZ-1.

Source Data Fig. 3c

Ammonia yield data with N2, unpurified air, Ar or O2 flow.

Source Data Fig. 3d

Ammonia yield data for 10 h with N2 flow.

Source Data Fig. 4b

Raman spectra data of NJUZ-1 measured at pristine state (saturated) and during the NRR process (unsaturated).

Source Data Extended Data Fig. 3a

IR spectra data of NJUZ-1 in air (black curve) and vacuum (dark cyan curve).

Source Data Extended Data Fig. 3b

Simulated IR spectrum data of C≡N bonds in NJUZ-1.

Source Data Extended Data Fig. 3c

Full Raman spectra data of 14N-NJUZ-1 and 15N-NJUZ-1.

Source Data Extended Data Fig. 3d

Simulated Raman spectrum data of Zn–C≡N–Zn structure.

Source Data Extended Data Fig. 3e

Experimental and simulated EPR spectrum data at low temperature (93 K) of NJUZ-1.

Source Data Extended Data Fig. 3f

EPR spectrum data of 15N-NJUZ-1.

Source Data Extended Data Fig. 6c

N2 adsorption isotherms data of NJUZ-1.

Source Data Extended Data Fig. 8a

Percentage of ammonia yield data with Air to N2 flow.

Source Data Extended Data Fig. 8b

25 h long-term ammonia yield data with N2 flow.

Source Data Extended Data Fig. 8d

XRD data of NJUZ-1 before and after 3, 10 and 25 h of the NRR in comparison with the simulated XRD pattern.

Source Data Extended Data Fig. 8g

Nitrogen adsorption–desorption isotherms data of NJUZ-1 before and after 25 test.

Source Data Extended Data Fig. 10d

Charge variation data of the N2-mHn species along the possible alternating, mixed and distal pathways.

Source Data Supplementary Fig. 2

TGA data of NJUZ-1.

Source Data Supplementary Fig. 6

Standard calibration data of NH4+.

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Xiong, Y., Li, B., Gu, Y. et al. Photocatalytic nitrogen fixation under an ambient atmosphere using a porous coordination polymer with bridging dinitrogen anions. Nat. Chem. 15, 286–293 (2023). https://doi.org/10.1038/s41557-022-01088-8

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