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Electrocatalytic nitrogen reduction reaction (NRR) is an appealing route for the sustainable NH3 synthesis, while developing efficient and durable NRR catalysts remains at the heart of achieving high-efficiency N2-to-NH3 electrocatalysis. Herein, we rationally combine vacancy and interface engineering to design sulfur-deficient Bi2S3 nanoparticles decorated Ti3C2Tx-MXene as an effective NRR catalyst. The developed Bi2S3 nanoparticles decorated Ti3C2Tx-MXene (Bi2S3-x/Ti3C2Tx) naturally contained abundant S-vacancies and exhibited a dramatically boosted NRR activity with an NH3 yield of 68.3 μg·h−1·mg−1 (−0.6 V) and a Faradaic efficiency of 22.5% (−0.4 V), far superior to pure Bi2S3 and Ti3C2Tx, and surpassing almost all ever reported Bi- and MXene-based NRR catalysts. Theoretical investigations unveiled that the exceptional NRR activity of Bi2S3-x/Ti3C2Tx stemmed from its dual-active-center system involving both S-vacancies and interfacial-Bi sites, which could synergistically promote N2 adsorption and *N2H formation to result in an energetic-favorable NRR process.
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