Graphitic carbon nitride supported Fe single-atom nanozymes synergize with nitrate reductase for photobiocatalytic nitrate conversion-Reference-Cited by-同舟云学术

Graphitic carbon nitride supported Fe single-atom nanozymes synergize with nitrate reductase for photobiocatalytic nitrate conversion

Published:2024-01-15 Issue: Volume: Page:
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Author:

An Xiaoqiang¹,Bian Jiyong¹,Zhao Jing¹,Lan Xianen¹,Liao Yang¹,Liu Ruiping¹,Liang Minmin²^ORCID,Tang Junwang³^ORCID,Liu Huijuan¹,Qu Jiuhui¹

Affiliation:

1. Tsinghua University

2. Beijing Institute of Technology

3. University College London

Abstract

Abstract Nitrate reduction is of paramount importance for both the restoration of natural ecosystems and the sustainable development of chemical industries, but faces challenges in the rate-limiting step of nitrate-nitrite conversion and the poor product selectivity of the multielectron reactions. Herein, we demonstrate a nitrate-to-nitrite photosynthesis route catalyzed by a biotic-abiotic nanoarchitecture composed of carbon nitride (C3N4) supported Fe single-atom nanozymes combined with native nitrate reductases. Under visible light irradiation, the photobiocatalyst exhibits a state-of-the-art capability for nitrate conversion, with nearly 100% selectivity of nitrate and an unprecedented reaction kinetic constant that far exceeds those of all reported visible-light-driven photocatalysts. The strong binding affinity of nanozyme to the reaction substrate contributes to the 68.9- and 20.2-fold enhancement in the activity compared to artificial C3N4 photocatalyst and natural NarGHI biocatalyst, respectively, far exceeding the biological enzymes and reported enzyme-mimicking nanomaterials for nitrate conversion. Mechanistic studies at the atomic- and molecular levels reveal that Fe single atoms and cyano (-C ≡ N) groups on C3N4 mimic the heme bD and heme bP in the NarI subunit and construct a unique electron transfer chain between the biotic-abiotic interface under visible light irradiation, contributing to efficient and selective nitrate reduction to nitrite via photobiocatalysis. This work represents a promising biotic-abiotic platform to address the bottleneck problems of nitrate conversion, offering new opportunities for the sustainable removal of nitrogen from water and ammonia energy production with low energy consumption and carbon emission.

Publisher

Research Square Platform LLC

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