水滑石限域Ni纳米颗粒催化氮甲基吲哚高效储氢

doi:10.6023/A25060229

摘要/Abstract

有机液态储氢(LOHC)技术通过含氮杂环有机物的催化加氢反应将氢气固定于液态介质中, 形成稳定的储氢载体, 是一种具有前景的新兴储氢策略. 然而, 该技术目前主要依赖贵金属催化剂, 基于廉价金属的高效催化体系研究尚显不足. 本研究采用Ni-Al层状双金属氢氧化物(NiAl-LDH)衍生镍基催化剂, 实现了氮甲基吲哚(NMID)的高效储氢(加氢). 系统考察了Ni/Al物质的量比及还原温度对催化性能的影响. 结果表明, NiAl-LDH在450 ℃还原制得的催化剂(Ni₂Al_1-re450)活性最优. 通过N₂物理吸附(BET)、X射线衍射(XRD)、X射线光电子能谱(XPS)及电感耦合等离子体发射光谱(ICP-OES)表征分析, 揭示其优异加氢活性源于较大的比表面积与较小的镍颗粒尺寸. 在优化反应条件下(150 ℃, 6 MPa H₂, 2 h, 间歇釜), Ni₂Al_1-re450可实现NMID的完全转化(100%), 8H-NMID产物收率达96.06%, 其性能显著优于商用0.5%Ru/Al₂O₃催化剂. 动力学研究表明, NMID加氢速率与温度呈正相关, 表观活化能为61.25 kJ/mol, 转化频率(TOF)达52.62 h⁻¹. 在微填充床反应器连续运行测试中(180 ℃, 6 MPa H₂), Ni₂Al_1-re450展现出优异的稳定性, 持续100 h反应期间, NMID转化率稳定在97%~100%, 8H-NMID选择性维持在97%~100%, 对应储氢容量达5.55% (w)~5.76% (w).

关键词: 有机液体储氢, 镍催化剂, 氮甲基吲哚, 镍铝水滑石

The advancement of non-noble metal catalysts holds immense importance for the broad industrial use of organic liquid hydrogen storage. In this study, Ni_aAl_b-layered double hydroxides (LDHs) were synthesized via co-precipitation method. Typically, a mixed solution of 100 mL Ni(NO₃)₂•6H₂O and Al(NO₃)₃•9H₂O was dropped into 100 mL Na₂CO₃ solution under vigorous stirring. The precipitation was carried out at room temperature, to achieve the desired pH value, a 3 mol/L NaOH solution was added to maintain the solution pH between 10±0.5. The resultant green precipitate underwent centrifugation and washing until nearly neutral, followed by drying for an extended period at 110 ℃. Thereafter, the sample was subjected to reduction at different temperatures for a duration of 2 h, with a meticulously controlled heating rate of 2.5 ℃/min. Finally, the influence of the Ni/Al ratio and reduction temperature on the catalytic activity was examined. The catalyst obtained by reducing NiAl-LDH at 450 ℃ (Ni₂Al_1-re450) exhibited the highest activity among the catalyst samples examined. Structural and compositional analyses of the catalyst were carried out using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectrometry (ICP-OES), and N₂ physisorption analysis (BET). The results indicated that the high hydrogenation activity of Ni₂Al_1-re450 was attributed to its larger specific surface area and smaller nickel particle size. Under the optimized reaction conditions (150 ℃, 6 MPa H₂, 2 h), the catalyst achieved a 100% conversion rate of NMID and a yield of 8H-NMID of 96.06% in a batch reactor, surpassing the commercial 0.5%Ru/Al₂O₃ hydrogenation catalyst. The hydrogenation reaction rate of NMID was positively correlated with temperature, with an apparent activation energy of 61.25 kJ/mol and a turnover frequency (TOF) of 52.62 h^－1. Moreover, Ni₂Al_1-re450 was continuously operated for 100 h in a micro packed-bed reactor under reaction conditions of 180 ℃ and 6 MPa. The results showed that the NMID conversion rate remained stable between 97%~100%, the selectivity for 8H-NMID was 97%~100%, and the hydrogen storage capacity was 5.55% (w)~5.76% (w).

Key words: organic liquid hydrogen storage, nickel catalyst, N-methylindole, nickel aluminum layered double hydroxide

引用此文

全洪林, 唐鋆磊, 张承志, 张恒溢, 李佳奇, 周太刚. 水滑石限域Ni纳米颗粒催化氮甲基吲哚高效储氢[J]. 化学学报, 2025, 83(11): 1340-1348.

Quan Honglin, Tang Junlei, Zhang Chengzhi, Zhang Hengyi, Li Jiaqi, Zhou Taigang. Hydrotalcite-Confined Ni Nanoparticles Catalyzed Efficient Hydrogen Storage of N-Methylindole[J]. Acta Chimica Sinica, 2025, 83(11): 1340-1348.

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图/表 7

图1. NiaAlb-LDH的XRD图谱

Figure 1. XRD patterns of NiaAlb-LDH catalysts

图2. (a) NiaAlb-LDH合成示意图; (b) Ni2Al1-re450的TEM图像

Figure 2. (a) A schematic diagram of NiaAlb-LDH synthesis; (b) TEM images of Ni2Al1-re450

图3. (a) N2吸附-脱附等温线; (b)所有样品的孔径分布; (c) Ni2Al1-re450的CO-TPD图谱; (d) Ni1Al2-re450, Ni1Al1-re450, Ni2Al1-re450和Ni3Al1-re450的XPS图谱

Figure 3. (a) N2 adsorption-desorption isotherm; (b) pore size distribution of all samples; (c) CO-TPD spectra of Ni2Al1-re450; (d) XPS Spectra of Ni1Al2-re450, Ni1Al1-re450, Ni2Al1-re450 and Ni3Al1-re450

Entry	Catalyst	S_BET^a/(m²•g^－1)	V_pore^b/(cm³•g^－1)	D_pore^c/nm	w_Ni^d/%	D_s^e
1	Ni₁Al_2-re450	135	0.14	3.8	—	—
2	Ni₁Al_1-re450	64	0.07	3.8	—	—
3	Ni₂Al_1-re450	142	0.28	5.3	53.28	0.5568
4	Ni₃Al_1-re450	68	0.21	9.6	—	—
5	Ni₂Al_1-re350	189	0.32	4.3	—	—
6	Ni₂Al_1-re550	130	0.27	6.5	—	—
7	Ni₂Al_1-re650	101	0.28	7.8	—	—

表1. 制备的催化剂样品的规格

Table 1. Specifications of the prepared catalyst samples

图4. (a) NMID氢化产物; (b)不同Ni/Al物质的量比; (c)不同还原温度; (d)不同反应温度; (e)反应时间对Ni2Al1-re450催化加氢NMID的影响; (f)与贵金属催化剂对比; (g)循环实验

Figure 4. (a) NMID hydrogenation products; (b) effect of different Ni/Al molar ratios; (c) effect of different reduction temperatures; (d) effect of different reaction temperatures; (e) effect of reaction time on Ni2Al1-re450 hydrogenation NMID; (f) comparison with noble metal catalysts; (g) cycle experiment; (reaction conditions: 0.2 g NMID, 20 mg catalyst)

图5. (a) ln(1－x)和反应时间之间的关系; (b) ln k和(1/T)之间的关系; (c)热过滤实验; (d), (e), (f) NMID在Ni2Al1-re450催化剂上的产物分布(100 ℃, 110 ℃, 130 ℃, 6 MPa H2). 反应条件: 0.2 g NMID, 20 mg催化剂

Figure 5. (a) Relationship between ln(1－x) and reaction time; (b) relationship between ln k and 1/T; (c) thermal filtration experiment; (d), (e), (f) product distribution over Ni2Al1-re450 catalyst at various temperatures (100 ℃, 110 ℃, 130 ℃, 6 MPa H2). Reaction conditions: 0.2 g NMID, 20 mg catalyst

图6. (a)微填充床加氢NMID示意图; (b)反应温度对NMID连续加氢的影响(反应条件: 催化剂装填量: 6 g Ni2Al1-re450, 系统压力: 6 MPa; 气体流速: 100 mL/min; 液体流速: 0.4 mL/min); (c)液体流速对NMID的影响(反应条件: 催化剂装填量: 6 g Ni2Al1-re450; 系统压力: 6 MPa; 气体流速: 100 mL/min; 反应温度: 180 ℃). (d), (e) Ni2Al1- re450上NMID加氢的长期稳定性测试(反应条件: 反应温度: 180 ℃; 液体流速: 0.05 mL/min; 系统压力: 6 MPa; 气体流速: 100 mL/min; 装入催化剂量: 6 g Ni2Al1-re450)

Figure 6. (a) Schematic diagram of hydrogenation NMID in Micro-packed bed reactor; (b) effect of reaction temperature on NMID continuous hydrogenation (reaction conditions: catalyst loading: 6 g Ni2Al1-re450; system pressure: 6 MPa; gas flow rate: 100 mL/min; liquid flow rate: 0.4 mL/min); (c) effect of liquid flow rate on NMID (reaction conditions: catalyst loading: 6 g Ni2Al1-re450; system pressure: 6 MPa; gas flow rate: 100 mL/min; reaction temperature: 180 ℃); (d), (e) long-term stability test for NMID hydrogenation over Ni2Al1-re450 (reaction conditions: reaction temperature: 180 ℃; gas flow rate: 100 mL/min; system pressure: 6 MPa; liquid flow rate: 0.05 mL/min; catalyst loading: 6 g Ni2Al1-re450)

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