K+-Intercalated carbon nitride with electron storage property for high-efficiency visible light driven nitrogen fixation

Dong, Gang; Qiu, Peng; Chen, Qingze; Huang, Cong; Chen, Feiyang; Liu, Xueqin; Li, Zhen; Wang, Yang; Zhao, Yanli

doi:10.1016/j.cej.2021.133573

Cited by 22 publications

(12 citation statements)

References 59 publications

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“…The peak at 1642 cm –1 appeared quickly due to the fast adsorption of N 2 on the surface of catalysts . The activation of N 2 led to the formation of the N–H stretching vibration at 3430 cm –1 . The two peaks at 1480 and 1145 cm –1 were detected as the H–N–H bending vibration and H 2 N–NH 2 stretching vibration from intermediate products, respectively .…”

Section: Results and Discussionmentioning

confidence: 99%

Porphyrin-Based Covalent Organic Frameworks Anchoring Au Single Atoms for Photocatalytic Nitrogen Fixation

et al. 2023

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The development of efficient photocatalysts for N2 fixation to produce NH3 under ambient conditions remains a great challenge. Since covalent organic frameworks (COFs) possess predesignable chemical structures, good crystallinity, and high porosity, it is highly significant to explore their potential for photocatalytic nitrogen conversion. Herein, we report a series of isostructural porphyrin-based COFs loaded with Au single atoms (COFX–Au, X = 1–5) for photocatalytic N2 fixation. The porphyrin building blocks act as the docking sites to immobilize Au single atoms as well as light-harvesting antennae. The microenvironment of the Au catalytic center is precisely tuned by controlling the functional groups at the proximal and distal positions of porphyrin units. As a result, COF1–Au decorated with strong electron-withdrawing groups exhibits a high activity toward NH3 production with rates of 333.0 ± 22.4 μmol g–1 h–1 and 37.0 ± 2.5 mmol gAu –1 h–1, which are 2.8- and 171-fold higher than that of COF4–Au decorated with electron-donating functional groups and a porphyrin–Au molecular catalyst, respectively. The NH3 production rates could be further increased to 427.9 ± 18.7 μmol g–1 h–1 and 61.1 ± 2.7 mmol gAu –1 h–1 under the catalysis of COF5–Au featuring two different kinds of strong electron-withdrawing groups. The structure–activity relationship analysis reveals that the introduction of electron-withdrawing groups facilitates the separation and transportation of photogenerated electrons within the entire framework. This work manifests that the structures and optoelectronic properties of COF-based photocatalysts can be finely tuned through a rational predesign at the molecular level, thus leading to superior NH3 evolution.

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Section: Results and Discussionmentioning

confidence: 99%

Porphyrin-Based Covalent Organic Frameworks Anchoring Au Single Atoms for Photocatalytic Nitrogen Fixation

et al. 2023

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“…Huang et al also fabricated both nitrogen vacancies and oxygen doping in hollow porous prismatic g-C 3 N 4 (Nv&Od-CN), which exhibited obvious improved photocatalytic nitrogen-fixation performance under visible-light irradiation (Figure d and e) . Dong et al demonstrated that the chemical adsorption function of the N 2 on K + -intercalated crystalline carbon nitride (KCCN) with abundant NVs (KCCN-NVs) was stronger than that on KCCN, suggesting that NVs promoted N 2 adsorption on the surface of the photocatalysts to improve their activities (Figure f and g) …”

Section: Construction Of Active Sites For Nrrmentioning

confidence: 99%

Section: Construction Of Active Sites For Nrrmentioning

confidence: 99%

“…119 Dong et al demonstrated that the chemical adsorption function of the N 2 on K + -intercalated crystalline carbon nitride (KCCN) with abundant NVs (KCCN-NVs) was stronger than that on KCCN, suggesting that NVs promoted N 2 adsorption on the surface of the photocatalysts to improve their activities (Figure 11f and g). 120 Similar to OVs and NVs, sulfur vacancies (SVs) also promote the cleavage of N�N bonds on the catalyst surface as active sites. Nanostructured metal sulfides, including onecomponent MoS 2 , 121−123 In 2 S 3 , 124 and FeS 2 , 125 two-component ZnIn 2 S 4 , 126 and three-component Zn 0.1 Sn 0.1 Cd 0.8 S, 127 have attracted considerable interest in the photocatalysis field.…”

Section: Vacancy Introductionmentioning

confidence: 99%

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Research Progress and Perspectives on Active Sites of Photo- and Electrocatalytic Nitrogen Reduction

et al. 2022

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Ammonia is closely relevant to human production and life. Although the widely used conventional Haber−Bosch process has a relatively high ammonia yield, it has obvious disadvantages of high energy consumption, serious pollution, and harsh reaction conditions. Compared with the Haber−Bosch process, photo-and electrocatalytic N 2 fixation has been demonstrated to be energy-saving, environmentally friendly, and economical because the ammonia can be generated under mild conditions. During the photo/electrocatalytic ammonia-production processes, sunlight or electricity is used as the renewable energy input, the atmosphere is used as the nitrogen source, and water is used as the proton source. However, the ammonia yields of the photo-and electrocatalytic nitrogen fixation are commonly low, which is mainly resulted by the lack of active sites to adsorb N 2 molecules and active N�N triple bonds. On the basis of the discussion about the importance of active sites for ammonia synthesis by summarizing the reaction mechanism of photo-and electrocatalytic methods, we outline the common methods of producing abundant active sites of N 2 adsorption and activation on the surface of catalysts, including vacancy introduction, heteroatom doping, cocatalyst support, and frustrated Lewis pairs construction. We also summarize the detection methods of ammonia, as well as other problems existing during the photo-and electrocatalytic nitrogen-fixation processes.

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“…The methods for fixing nitrogen to produce ammonia are an important topic. 1–4 Early in the 20th century, industrial NH 3 synthesis began with the introduction of the Haber–Bosch process, which remains the main technology in industrial NH 3 production today. This process requires iron-based compounds as heterogeneous catalysts, and nitrogen and hydrogen are introduced to synthesize ammonia under the conditions of high temperature (623–823 K) and high pressure (150–350 atm).…”

Section: Introductionmentioning

confidence: 99%

The order of loading affects photocatalytic nitrogen fixation activity of the ternary composites of PdO/Au–TiO₂

Wang

Liu

et al. 2023

New J. Chem.

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K+-Intercalated carbon nitride with electron storage property for high-efficiency visible light driven nitrogen fixation

Cited by 22 publications

References 59 publications

Porphyrin-Based Covalent Organic Frameworks Anchoring Au Single Atoms for Photocatalytic Nitrogen Fixation

Porphyrin-Based Covalent Organic Frameworks Anchoring Au Single Atoms for Photocatalytic Nitrogen Fixation

Research Progress and Perspectives on Active Sites of Photo- and Electrocatalytic Nitrogen Reduction

The order of loading affects photocatalytic nitrogen fixation activity of the ternary composites of PdO/Au–TiO₂

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K+-Intercalated carbon nitride with electron storage property for high-efficiency visible light driven nitrogen fixation

Cited by 22 publications

References 59 publications

Porphyrin-Based Covalent Organic Frameworks Anchoring Au Single Atoms for Photocatalytic Nitrogen Fixation

Porphyrin-Based Covalent Organic Frameworks Anchoring Au Single Atoms for Photocatalytic Nitrogen Fixation

Research Progress and Perspectives on Active Sites of Photo- and Electrocatalytic Nitrogen Reduction

The order of loading affects photocatalytic nitrogen fixation activity of the ternary composites of PdO/Au–TiO2

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The order of loading affects photocatalytic nitrogen fixation activity of the ternary composites of PdO/Au–TiO₂