Regulating the Unsaturated Co Sites on MOF-74(Co) for Enhancing Photocatalytic N2 to NH3 Conversion

IF 7.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Binghua Ye, Cheng Liu, Yueling Chen, Qi Chen, Kaiqiang Jing, Jimmy C. Yu, Jionghua Wu* and Ling Wu*, 
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Abstract

Photocatalytic N2 fixation is a green and sustainable pathway for the synthesis of ammonia. However, its efficiency is considerably restricted by the energy-intensive activation of N2 molecules. Herein, a series of MOF-74(Co) with varying contents of coordinatively unsaturated Co sites were synthesized through the thermal treatment at different temperatures (T = 100, 150, 200, 250 °C). These photocatalysts were used for the photocatalytic fixation of N2 in the absence of a sacrificial agent. The experimental results and theoretical computations indicate that the amount of coordinatively unsaturated Co sites increases as the temperature elevates by the removal of coordinated H2O from MOF-74(Co). These Co sites can function as active sites to promote chemisorption and activation of N2 molecules. The sample MOF-74(Co)-200 exhibits the highest NH4+ production rate of 84 μmol·g–1·h–1, which is six times higher than that of the pristine MOF-74(Co) (13.9 μmol·g–1·h–1). The enhanced performance can be ascribed to the abundance of active sites and the optimal mobility of the photogenerated charges. Finally, a mechanism is proposed for the photocatalytic N2 activation at the molecular level.

Abstract Image

光催化固定 N2 是合成氨的一种绿色可持续途径。然而,由于激活 N2 分子需要消耗大量能量,因此其效率受到很大限制。在此,通过在不同温度(T = 100、150、200、250 °C)下进行热处理,合成了一系列具有不同配位不饱和 Co 位点含量的 MOF-74(Co)。这些光催化剂被用于在没有牺牲剂的情况下光催化固定 N2。实验结果和理论计算表明,随着温度的升高,MOF-74(Co)中配位的 H2O 被去除,配位不饱和 Co 位点的数量也随之增加。这些 Co 位点可作为活性位点,促进 N2 分子的化学吸附和活化。MOF-74(Co)-200 样品的 NH4+ 生成率最高,达到 84 μmol-g-1-h-1,是原始 MOF-74(Co) 样品(13.9 μmol-g-1-h-1)的六倍。性能的提高可归因于活性位点的丰富和光生电荷的最佳流动性。最后,提出了光催化 N2 在分子水平上的活化机制。
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来源期刊
ACS Sustainable Chemistry & Engineering
ACS Sustainable Chemistry & Engineering CHEMISTRY, MULTIDISCIPLINARY-ENGINEERING, CHEMICAL
CiteScore
13.80
自引率
4.80%
发文量
1470
审稿时长
1.7 months
期刊介绍: ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment. The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.
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