介孔氧化镍纳米片负载Pt纳米粒子电催化合成氨

doi:10.1016/S1872-2067(21)63877-9

催化学报 ›› 2022, Vol. 43 ›› Issue (5): 1371-1378.DOI: 10.1016/S1872-2067(21)63877-9

• 论文 • 上一篇

介孔氧化镍纳米片负载Pt纳米粒子电催化合成氨

熊伟^a(), 周敏^a, 李昊^b(), 丁朝^c, 张达^d, 吕耀康^e

^a武汉工程大学化学与环境工程学院, 湖北省新型反应器与绿色化学工艺重点实验室, 磷资源开发利用教育部工程研究中心, 绿色化工过程教育部重点实验室, 湖北武汉430205, 中国
^b丹麦科技大学物理系, 林比, 丹麦
^c武汉科技大学先进材料与纳米技术研究院, 耐火材料与冶金国家重点实验室, 湖北武汉430071, 中国
^d长江科学研究院, 湖北武汉430071, 中国
^e浙江工业大学化工学院, 浙江杭州310014, 中国

收稿日期:2021-05-25 接受日期:2021-06-18 出版日期:2022-05-18 发布日期:2022-03-23
通讯作者: 熊伟,李昊
基金资助:
国家自然科学基金(21703161);浙江省自然基金(LY19B010003)

Electrocatalytic ammonia synthesis catalyzed by mesoporous nickel oxide nanosheets loaded with Pt nanoparticles

Wei Xiong^a(), Min Zhou^a, Hao Li^b(), Zhao Ding^c, Da Zhang^d, Yaokang Lv^e

^aKey Laboratory for Green Chemical Process (Ministry of Education), Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education, Hubei Key Laboratory Of Novel Reactor &Green Chemical Technology, School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430205, Hubei, China
^bDepartment of Physics, Technical University of Denmark, Lyngby 2800, Denmark
^cThe State Key Laboratory of Refractories and Metallurgy, Institute of Advanced Materials and Nanotechnology, Wuhan University of Science and Technology, Wuhan 430071, Hubei, China
^dChangjiang River Scientific Research Institute, Wuhan 430071, Hubei, China
^eCollege of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2021-05-25 Accepted:2021-06-18 Online:2022-05-18 Published:2022-03-23
Contact: Wei Xiong, Hao Li
Supported by:
National Natural Science Foundation of China(21703161);Zhejiang Provincial Natural Science Foundation of China(LY19B010003)

摘要/Abstract

摘要：

由于NiO成本低且3d轨道具有可调谐的八电子结构, 被公认为是温和条件下电化学氮还原反应(NRR)的有效电催化剂之一. 然而, 由于过渡金属氧化物电催化剂的电导率相对较低, 阻碍了其在该领域的应用. 贵金属具有良好的电导率, 通常可用于构建异质材料, 利用协同作用, 来提高载体材料的电导率并改善电催化性能. 因此, 在氧化镍上嵌入或掺杂具有催化性能的高导电金属是获得高性能NRR电催化剂的一种有效方法. 在早期的研究中, 由于贵金属基催化剂(Au, Pd和Ru)导电性好, 一般都具有较好的电化学NRR活性. 值得注意的是, 尽管Pt在其它电催化过程中表现出优异的电催化活性, 但很少有关于NRR的Pt基电催化剂的报道. 这主要是因为Pt基电催化剂具有较强的催化析氢反应活性. 因此, 研究Pt基NRR电催化剂的结构, 以构建高效的Pt基NRR催化剂, 是一个有意义且具有挑战性的研究课题. 迄今为止, 关于Pt/NiO复合材料对NRR催化活性的研究报道较少. 基于此, 本文使用纯的氧化镍纳米片作为载体来负载不同含量的Pt纳米粒子, 利用Pt的高导电性与NiO的可调谐电子特性的协同作用来提高NRR活性.

本文通过简单的还原法成功合成了Pt/NiO-NSs, 采用透射电镜、X射线光电子能谱(XPS)、密度泛函理论(DFT)计算、紫外可见光谱等表征手段研究了不同Pt负载量对NRR活性的影响. 与纯NiO相比, 用少量铂纳米粒子(3~10 nm)掺杂氧化镍纳米片(Pt/NiO-NSs)可显著提高纯NiO的法拉第效率(FE)和氨产率, 打破了商用Pt基电催化剂几乎没有NRR潜力的普遍观点. 电催化实验结果表明, 在‒0.2 V vs RHE的0.1 mol/L Na₂SO₄溶液中, 样品Pt/NiO-2表现出20.59 μg h^‒1 mg^‒1_cat.的氨产率和15.56%的FE, 分别是相同外加电位下纯NiO纳米片的5倍(3.79 μg h^‒1 mg^‒1_cat)和3倍(5.97%)左右. XPS分析结果表明, Pt/NiO-NSs中Pt的价态为Pt⁰, Pt²⁺和Pt⁴⁺, 其中Pt/NiO-2具有较高含量的高氧化态Pt物种, 从而有利于N₂化学吸附和活化. DFT结果表明, 与纯Pt相比, 负载在NiO基底上的Pt纳米粒子的d带电子更接近费米能级, 为NRR提供了更有利的电子结构. 该研究表明, 当Pt负载在合适的基底上时, 可成为有效的NRR电化学催化剂. 综上, 本文为制备高NRR活性的Pt基电催化剂提供了一种新的策略.

关键词: 铂纳米粒子, 氧化镍纳米片, 氮还原反应, 电催化

Abstract:

Owing to its cost-effectiveness and adjustable eight-electron distribution in the 3d orbital, nickel oxide (NiO) is considered an effective electrocatalyst for an ambient electrochemical nitrogen reduction reaction (NRR). However, because of the low conductivity of the transition metal oxide electrocatalyst, its application in this field is limited. In this study, we found that the doping of NiO nanosheets with a small amount (3-10 nm) of Pt nanoparticles (Pt/NiO-NSs) leads to considerable improvements in the Faradaic efficiency (FE) and NH₃ yield compared with those obtained using pure NiO, breaking the common perception that commercial Pt-based electrocatalysts demonstrate little potential for NRR due to their high hydrogen evolution tendency. In a 0.1 mol/L Na₂SO₄ solution at -0.2 V vs. RHE, a typical Pt/NiO-2 sample exhibits an optimum electrochemical NH₃ yield of 20.59 μg h^-1 mg^-1_cat. and an FE of 15.56%, which are approximately 5 and 3 times greater, respectively, than those of pure NiO nanosheets at the same applied potential. X-ray photoelectron spectroscopy analysis revealed that Pt in Pt/NiO-NSs exist as Pt⁰, Pt²⁺, and Pt⁴⁺ and that high-valence Pt ions are more electropositive, thereby favoring chemisorption and the activation of N₂ molecules. Density function theory calculations showed that the d-band of Pt nanoparticles supported on NiO is significantly tuned compared to that of pure Pt, affording a more favorable electronic structure for NRR. The results of this study show that Pt can be an effective NRR electrochemical catalyst when loaded on an appropriate substrate. Most importantly, it provides a new synthetic avenue for the fabrication of highly active Pt-based NRR electrocatalysts.

Key words: Platinum nanoparticles, NiO nanosheets, Nitrogen reduction reaction, Electrocatalysis

熊伟, 周敏, 李昊, 丁朝, 张达, 吕耀康. 介孔氧化镍纳米片负载Pt纳米粒子电催化合成氨[J]. 催化学报, 2022, 43(5): 1371-1378.

Wei Xiong, Min Zhou, Hao Li, Zhao Ding, Da Zhang, Yaokang Lv. Electrocatalytic ammonia synthesis catalyzed by mesoporous nickel oxide nanosheets loaded with Pt nanoparticles[J]. Chinese Journal of Catalysis, 2022, 43(5): 1371-1378.

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图/表 9

Fig. 1. TEM images of NiO (a), Pt/NiO-1 (b), Pt/NiO-2 (c), Pt/NiO-3 (d); HRTEM (e), and EDS (f) images for Pt/NiO-2.

Fig. 2. XRD patterns (a) and XPS spectra (b) of Pt 4f of Pt/NiO-NSs; (c) Corresponding XPS spectra for Ni 2p; (d) Corresponding XPS spectra for O 1s.

Table 1 Surface contents of Pt0 and Ptδ+ species in samples.

Catalysts	Pt⁰/%	Pt^δ⁺ (Pt²⁺, Pt⁴⁺)/%
Pt/NiO-1	50.0	50.0
Pt/NiO-2	46.7	53.3
Pt/NiO-3	51.7	49.3

Fig. 3. (a) LSV curves of Pt/NiO-1, Pt/NiO-2, and Pt/NiO-3 in N2-saturated 0.1 mol/L Na2SO4; LSV curves of Pt/NiO-1 (b), Pt/NiO-2 (c), and Pt/NiO-3 (d) both measured in an N2-saturated (red line) and Ar-saturated (black line) 0.1 mol/L Na2SO4.

Fig. 4. Electroreduction of N2 to NH3 on Pt/NiO-NSs electrocatalysts. (a) UV-vis absorption spectra of NH3; (b) Corresponding NRR performance of different electrocatalysts at -0.2 V vs. RHE.

Fig. 5. (a) UV-vis absorption spectra of Pt/NiO-2 in N2-saturated 0.1 mol/L Na2SO4 at various potentials; (b) corresponding NH3 yields and FEs of Pt/NiO-2 for NRR; (c) Corresponding UV-vis absorption spectra of N2H4.

Table 2 NRR performance comparison of other electrocatalysts.

Catalyst	Electrolyte	Yield (μg h^-1 mg^-1_cat.)	FE (%)	Ref.
Pd	0.1 mol/L PBS	4.5	8.2	[34]
Pd-Ag-S	0.1 mol/L Na₂SO₄	9.73	18.41	[35]
pAu/NF Pd-Co/CuO	0.1 mol/L Na₂SO₄ 0.1 mol/L KOH	9.42 10.04	13.36 2.16	[36] [37]
Mn₃O₄@rGO	0.1 mol/L Na₂SO₄	17.4	3.52	[38]
N-C@NiO/GP La₂O₃ Fe₂O₃ Cr₂O₃-rGO CoO QD/RGO CoP HNC F-SnO₂/CC	0.1 mol/L HCl 0.1 mol/L Na₂SO₄ 0.1 mol/L Na₂SO₄ 0.1 mol/L HCl 0.1 mol/L Na₂SO₄ 1.0 mol/L KOH 0.1 mol/L Na₂SO₄	14.022 17.04 15.9 33.3 21.5 10.78 19.3	30.43 4.76 0.94 7.3 8.3 7.36 8.6	[39] [40] [41] [42] [43] [44] [45]
Pt/NiO	0.1 mol/L Na₂SO₄	20.59	15.56	This work

Fig. 6. (a) NH3 yields of Pt/NiO-2 in N2- and Ar-saturated 0.1 mol/L Na2SO4 solutions, N2-saturated 0.1 mol/L Na2SO4 solution at open circuit, and N2-saturated 0.1 mol/L Na2SO4 solution at blank carbon paper; (b) Chronoamperometry test results of Pt/NiO-2 at various potentials; (c) Cycling test results of Pt/NiO-2 at -0.2 V vs. RHE.

Fig. 7. Calculated PDOS of Pt(111) (a) and Pt nanocluster (b) supported on NiO(100). Insets show the top and side views of the DFT-optimized Pt/NiO(100) structure. Grey, green, and red spheres represent Pt, Ni, and O, respectively.

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介孔氧化镍纳米片负载Pt纳米粒子电催化合成氨

Electrocatalytic ammonia synthesis catalyzed by mesoporous nickel oxide nanosheets loaded with Pt nanoparticles

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