电化学制备超细g-C<sub>3</sub>N<sub>4</sub>量子点及其电催化析氢性能

YANG Na-na; CHEN Zhi-gang; ZHAO Zhi-gang; CUI Yi

doi:10.1016/S1872-5805(21)60045-8

电化学制备超细g-C₃N₄量子点及其电催化析氢性能

doi: 10.1016/S1872-5805(21)60045-8

杨娜娜^{1, 2,},
陈志刚¹,
赵志刚^{1, 2},
崔义^{1, 2, ,}

1.
中国科学技术大学纳米技术与纳米仿生学院，安徽合肥 230026
2.
中国科学院苏州纳米技术与纳米仿生研究所，江苏苏州 215123

基金项目: 国家自然科学基金 (91845109, 21872169, 22109171, 22172190)；中科院稳定支持基础研究领域青年团队计划（YSBR-022），中科院青年交叉团队项目（JCTD-2021-14），江苏省博士后科研资助计划项目（2021K226B）

详细信息

通讯作者:
崔　义，研究员. E-mail：ycui2015@sinano.ac.cn

中图分类号: TQ127.1⁺1
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出版历程
- 收稿日期: 2021-03-09
- 修回日期: 2021-05-07
- 网络出版日期: 2021-06-03
- 刊出日期: 2022-03-30

Electrochemical fabrication of ultrafine g-C₃N₄ quantum dots as a catalyst for the hydrogen evolution reaction

YANG Na-na^{1, 2
,},
CHEN Zhi-gang¹,
ZHAO Zhi-gang^{1, 2},
CUI Yi^{1, 2
, ,}

1.
School of Nano-Tech and Nano-Bionics, University of Science and Technology of China, Hefei 230026, China
2.
Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China

Funds: We would like to acknowledge the financial support from Natural Science Foundation of China (91845109, 21872169, 22109171, 22172190), Y.C. would like to acknowledge the support from the CAS Project for Young Scientists in Basic Research (YSBR-022) and the Young Cross Team Project of CAS (JCTD-2021-14). Z.C. would like to acknowledge the support from Jiangsu Planned Projects for Postdoctoral Researc Funds (2021K226B)

More Information

Author Bio:
杨娜娜，硕士研究生. E-mail：nnyang2019@sinano.ac.cn

Corresponding author: CUI Yi, Professor. E-mail: ycui2015@sinano.ac.cn

摘要

摘要: 由于其高含量的面内氮元素、优异的化学和热力学稳定性、可调的电子能带结构和环境友好的特点，石墨相结构的氮化碳（g-C₃N₄）材料作为一种非金属催化剂在光电催化领域已引起广泛关注。相较于光催化领域能带结构的调控，g-C₃N₄在电催化领域的设计主要集中在活性位点的构筑和电子转移能力的调节。本文报道了一种三价Al³⁺离子电化学插层超快制备超细g-C₃N₄量子点（QDs）的剥离策略，与传统的碱金属离子相比，Al³⁺带电荷量大、冲击能力强，易于得到粒径和厚度更小的均一量子点材料。相应的透射电镜（TEM），原子力显微镜（AFM）和紫外吸收光谱仪（UV-vis）表征证实了所制g-C₃N₄ QDs的平均粒径只有3.5 nm，厚度只有3个C―N原子层（~1 nm），并且富含C/N缺陷。这种超细且富含缺陷的量子点材料在0.5 mol L⁻¹ H₂SO₄电解液中具有接近0 V的电催化析氢（HER）开口电位、优异的过电位（η₁₀=208 mV）和较低的塔菲尔斜率（b=52 mV·dec⁻¹）。这项工作提出的快速制备富含C/N缺陷g-C₃N₄ QDs的策略也为研究其它二维层状材料的剥离及其在电催化领域的应用提供了一条有趣的研究思路，有利于发掘二维材料更多丰富的物化性质。
- g-C₃N₄ /
- 电化学剥离 /
- Al³⁺离子 /
- 量子点 /
- 电催化析氢
Abstract: Because of its high concentration of in-plane elemental nitrogen, superior chemical/thermal stability, tunable electronic band structure and environmentally friendly nature, graphite-like carbon nitride (g-C₃N₄) is a new promising metal-free material that has drawn much attention in photo-/electric catalysis. Compared with the regulation of the band structure in photocatalysis, the deliberate synthesis of g-C₃N₄ electrocatalysts is mainly focused on the construction of catalytic sites and the modulation of the charge transfer kinetics. This work reports a rapid method for synthesizing ultrafine g-C₃N₄ quantum dots (QDs) by electrochemical exfoliation using Al³⁺ ions as an intercalation agent. Uniform g-C₃N₄ QDs with small lateral size and thickness were collected more easily due to the higher charge density and stronger electrostatic force of Al³⁺ ions in the lattice of the host material, compared to conventional univalent alkali cations. The QDs had an average lateral dimension and thickness of 3.5 nm and 1.0 nm, respectively, as determined by TEM and AFM measurements. The presence of a large number of C/N defects was verified by the UV-vis spectra. The ultrafine g-C₃N₄ QDs had a superior hydrogen evolution reaction performance with an ultra-low onset-potential approaching 0 V, and a low overpotential of 208 mV at 10 mA cm⁻², as well as a remarkably low Tafel slope (52 mV·dec⁻¹) in an acidic electrolyte.
- g-C₃N₄ /
- Electrochemical exfoliation /
- Al³⁺ ions /
- QDs /
- HER

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FIG. 1403. FIG. 1403.

FIG. 1403..

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Figure 1. (a) Schematic illustration of the electrochemical intercalation of Al³⁺ cations into the interlayer of bulk g-C₃N₄ materials. (b) The extraction of Al³⁺ ions wrapped by oleic acid molecules from the g-C₃N₄ lattice for the fabrication of the ultrafine g-C₃N₄ QDs by the sonication process. (c) Typical optical images of bulk g-C₃N₄ and g-C₃N₄ QDs.

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Figure 2. (a) XRD patterns of bulk g-C₃N₄ and g-C₃N₄ QDs. (b)TEM image of g-C₃N₄ QDs, with the corresponding SAED pattern in the insert. (c) EDS image of g-C₃N₄ QDs. (d) Statistic analysis of the lateral dimension of the as-obtained g-C₃N₄ QDs. (e) HRTEM image of g-C₃N₄ QDs. (f) AFM image of g-C₃N₄ QDs. (g) Thickness of g-C₃N₄ QDs highlighted in line 1 and line 2 in (f).

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Figure 3. (a) Raman spectra and (b) UV−vis absorbance spectra of g-C₃N₄ and g-C₃N₄ QDs, with the corresponding band gap inserted in (b).

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Figure 4. (a) Polarization (LSV) curves and (b) Tafel plots for as-obtained g-C₃N₄ QDs, bulk material and benchmark Pt/C at a scan rate of 5 mV s⁻¹ in 0.5 mol L⁻¹ H₂SO₄ solutions. (c) Comparison of the HER performance obtained from g-C₃N₄ QDs and other previous reports. (d) Nyquist plots and (e) chronopotentiometry measurements of g-C₃N₄ QDs and bulk material.

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Table 1. A comparison of the merits and demerits of different g-C₃N₄QDs preparation methods.

Methods	Particle size(nm)	Thickness(nm)	Advantages	Disadvantages	Ref.
Sonication method	Below 10	5–6	Simple procedures and facile operation	Low yield and long circle	[35,36]
Sonication along with chemical oxidation	4	0.35	High yield and high purity	High cost and complex operation	[37,38]
Hydrothermal method	3.3	2	Simple procedures and low cost	Low yield and long circles	[39,40]
Hydrothermal along with chemical oxidation	5-9	Below 10	High yield and high purity	High cost and complex operation	[41,42]
Solid-phase method	4.3	1.5–2.5	High yield	Complex purification and long circles	[43,44]
Microwave-assisted solvothermal method	1-5	-	Simple procedures, short circles and low cost	Low quantum yield	[45,46]
Quasi-chemical vapor deposition (CVD) method	2.4	-	Closely integrated	Energy-consuming and complex purification	[47]
Electrochemical exfoliation	3.5	1	Simple procedures, facile operation, short circles, high yield and high purity	No more experimental exploration for the intercalation mechanism	This work

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