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摘要: 硝酸根还原反应(NtRR)是一种合成氨(NH3)的有效方法。催化剂的合成包括2步简单的工艺：首先在炭布（CC）上合成Co3O4纳米线，然后以六乙炔基苯(HEB)为前驱体在Co3O4表面生长石墨炔(GDY)(110 °C, 10 h)，从而可控合成Co3O4/GDY纳米线异质结催化剂。高分辨率扫描电镜(SEM)、透射电镜(HRTEM)、X射线光电子能谱(XPS)和拉曼表征等证实了Co3O4/GDY异质界面的成功合成，界面处形成的独特的sp-C―Co键以及GDY与Co之间的不完全电荷转移为催化反应提供了持续的电子供应，保证了NtRR的高效进行。Co3O4/GDY在NtRR中展现了优异催化性能，其NH3产率（YNH3）和法拉第效率（FE）分别达到了0.78 mmol h−1 cm−2 和92.45%。这项工作为在温和条件下，从废水中高性能生产氨的异质结构提供了一种通用方法。Abstract: The nitrate reduction reaction (NtRR) has been demonstrated to be a promising way for obtaining ammonia (NH3) by converting NO3− to NH3. Here we report the controlled synthesis of cobalt tetroxide/graphdiyne heterostructured nanowires (Co3O4/GDY NWs) by a simple two-step process including the synthesis of Co3O4 NWs and the following growth of GDY using hexaethynylbenzene as the precursor at 110 °C for 10 h. Detailed scanning electron microscopy, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman characterization confirmed the synthesis of a Co3O4/GDY heterointerface with the formation of sp-C―Co bonds at the interface and incomplete charge transfer between GDY and Co, which provide a continuous supply of electrons for the catalytic reaction and ensure a rapid NtRR. Because of these advantages, Co3O4/GDY NWs had an excellent NtRR performance with a high NH3 yield rate (YNH3) of 0.78 mmol h−1 cm−2 and a Faraday efficiency (FE) of 92.45% at −1.05 V (vs. RHE). This work provides a general approach for synthesizing heterostructures that can drive high-performance ammonia production from wastewater under ambient conditions.
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Key words:
- Graphdiyne /
- Heterostructures /
- Electrocatalysis /
- Nitrate reduction reaction /
- Ammonia production
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Figure 2. Morphological characterizations of samples. (a) Low- and (b, c) high-magnification SEM images of the Co3O4. (d) Low- and (e, f) high-magnification SEM images of the as-prepared Co3O4/GDY. (g) EDS mapping of C, O and Co in Co3O4/GDY nanowires. (h) Contact angle measurements of Co3O4/GDY. (i) Optical photos of Co3O4/GDY
Figure 3. (a-c) HRTEM images of the Co3O4. (d-f) HRTEM images of the Co3O4/GDY. (e) The high distribution of Co3O4 in Co3O4/GDY. (f) Boundary between Co3O4 and GDY. (g) Low- and (h, i) high-magnification HRTEM images of GDY on the surface of Co3O4/GDY
Figure 4. (a) Raman spectra of Co3O4 and Co3O4/GDY. (b) C 1s XPS spectra of Co3O4 and Co3O4/GDY. (c) Co 2p XPS spectra of Co3O4 and Co3O4/GDY. (d) O 1s XPS spectra of Co3O4 and Co3O4/GDY. OⅠ represents the Co-O bond; OⅡ is assigned as the ―OH on the surface; OⅢ is considered to originate from environmental contamination. (e) Schematic illustration of the electron transfer at the GDY-Co3O4 interfaces of Co3O4/GDY. (f) The current density differences (Δj= ja−jc) are plotted against scan rates. (g) Nyquist plots of Co3O4 and Co3O4/GDY. (h) Co 2p XPS spectra of Co3O4/GDY after NtRR. (i) Schematic diagram of charge changes in Co3O4/GDY during the NtRR process
Figure 5. NtRR performance tests. (a) Schematic representation of the NO3−-to-NH3 conversion. (b) Linear sweep voltammetry curves of the samples in 0.5 mol L−1 K2SO4 +0.1 mol L−1 NO3−+ and pure 0.5 mol L−1 K2SO4 aqueous solutions. (c) Current density-time curves of Co3O4/GDY at different potentials in 0.5 mol L−1 K2SO4 + 0.1 mol L−1 NO3−. The YNH3 and FE of (d) Co3O4 and (e) Co3O4/GDY in 0.5 mol L−1 K2SO4 + 0.1 mol L−1 NO3−. (f) Stability tests of Co3O4/GDY at −1.05 V (vs. RHE). (g) YNH3 and FE of Co3O4/GDY at −1.05 V (vs. RHE) with and without NO3−. (h) Proportion of products. (i) NtRR performance comparison to other catalysts. (j-l) Insitu ATR-FTIR spectra of Co3O4/GDY during NtRR
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