Y2O3负载金属Cu在催化甲醛水溶液制氢反应中的Y2O3载体效应

doi:10.7503/cjcu20170065

摘要/Abstract

摘要：

采用NaBH₄还原法将纳米金属Cu负载在Y₂O₃上. 通过X射线衍射(XRD)、 X射线光电子能谱(XPS)、透射电子显微镜(TEM)和测定氢氧根在Y₂O₃和Cu上的吸附等手段对样品进行了表征. 结果表明, Y₂O₃表面存在一层薄的Y(OH)₃, 能优先吸附OH^-使其在Y₂O₃表面“富集”; 金属Cu以纳米粒子形式负载在Y₂O₃上. 在碱性甲醛溶液中考察了Y₂O₃负载Cu(Cu/Y₂O₃)的催化性能. 结果表明, 在低碱度条件下, 相对于未负载纳米Cu的Y₂O₃, Cu/Y₂O₃具有较高的产氢活性. 当氢氧化钠浓度为0.050 mol/L时, 在氮气气氛下Cu/Y₂O₃产氢量约为未负载纳米Cu的7.8倍; 而在空气气氛下约为4.3倍. 在2种气氛下, Cu/Y₂O₃产氢的最佳氢氧化钠浓度均为0.25 mol/L. 这可归结为Y₂O₃表面对OH^-的“富集”效应, 使其表面产生更多的活性物种CH₂(OH)O^-(甲二醇负离子). 相对于未负载纳米Cu的Y₂O₃, Y₂O₃负载Cu提高了催化剂的稳定性, 其原因是Y₂O₃负载阻止了Cu粒子在反应过程的生长.

关键词: 甲醛, 制氢, 负载铜, Y₂O₃, OH-富集

Abstract:

Nano metal Cu was loaded on Y₂O₃ by NaBH₄ reduction method. The sample was characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM) and adsorption measurement of OH^- on Y₂O₃ and Cu. The results show that there is a thin layer of Y(OH)₃ on the surface of Y₂O₃, which can preferentially adsorb OH^-, that is, “enrichment” of OH^- on Y₂O₃; metal Cu was loaded on Y₂O₃ in the form of nano particles. The performance of Cu supported on Y₂O₃(Cu/Y₂O₃) catalyst was investigated in alkaline formaldehyde solution. The results show that under low alkalinity, Cu/Y₂O₃exhibits higher activity for hydrogen production than unloaded nano metal Cu. When the concentration of NaOH is 0.050 mol/L, the hydrogen amount produced over Cu/Y₂O₃ is 7.8 times as high as that over nano Cu under N₂ atmosphere, whereas the former is 4.3 times as high as the latter under air atmosphere. The optimal NaOH concentration for hydrogen production over Cu/Y₂O₃ is 0.25 mol/L under both atmospheres. The results can be attributed to “enrichment” effect of OH^- on Y₂O₃, leading to production of the higher concentration of active CH₂(OH)O^-(formaldehyde anion) species on Y₂O₃. The stability of Cu/Y₂O₃ is improved compared with that of unloaded nano Cu. The reason is that the load of Cu on Y₂O₃ prevents growth of Cu particles during the reaction.

Key words: Formaldehyde, Hydrogen production, Load of Cu, Y₂O₃, Enrichment of OH-

中图分类号:

O643

TrendMD:

田毅, 李越湘, 彭绍琴. Y₂O₃负载金属Cu在催化甲醛水溶液制氢反应中的Y₂O₃载体效应. 高等学校化学学报, 2017, 38(10): 1841.

TIAN Yi, LI Yuexiang, PENG Shaoqin. Effect of Y₂O₃ Supporter on the Catalytic Hydrogen Production from an Aqueous Formaldehyde Solution Catalyzed by Metal Cu Loaded on Y₂O₃^†. Chem. J. Chinese Universities, 2017, 38(10): 1841.

图/表 11

Fig.1 XRD patterns of 10-Cu/Y2O3 and nano Cu(inset)

Fig.2 High-resolution XPS spectra of Cu2p32(A) and O1s(B) of 10-Cu/Y2O3

Fig.3 TEM images of Y2O3(A), nano Cu(B), 10-Cu/Y2O3(C) and size distribution histograms of nano Cu(D1), 10-Cu/Y2O3(D2)

Fig.4 Adsorption isotherms of OH- on Y2O3(A), nano Cu(B) and 10-Cu/Y2O3(C)The insets are the linear plots of 1/qe vs. 1/ce.

Fig.5 Effects of Cu loading of x-Cu/Y2O3(A) and formaldehyde concentration(B) on hydrogen generation under N2 atmosphere(A) x(%): a. 5; b. 10; c. 15; d. 20. Reaction conditions: 0.50 mol/L of NaOH; 0.60 mol/L of HCHO; a given amount of x-Cu/Y2O3 Cu containing 5 mg Cu. (B) cHCHO/(mol·L-1): a. 0.10; b. 0.30; c. 0.60; d. 0.90; e. 1.20. Reaction conditions: 0.50 mol/L of NaOH; 50 mg of 10-Cu/Y2O3.

Fig.6 Effect of NaOH concentration on hydrogen generation over nano Cu(A) and 10-Cu/Y2O3(B) under N2 atmospherecNaOH/(mol·L-1): a. 0; b. 0.05; c. 0.10; d. 0.25; e. 0.50. Reaction conditions: 0.60 mol/L of HCHO;5 mg of nano Cu or 50 mg of 10-Cu/Y2O3.

Fig.7 Effect of NaOH concentration on hydrogen generation over nano Cu(A) and 10-Cu/Y2O3(B) under air atmospherecNaOH/(mol·L-1): a. 0.05; b. 0.10; c. 0.25; d. 0.50. Reaction conditions are the same as those in Fig.6.

Table 1 Comparison of minimum and optimal(used) NaOH concentrations and optimal H2 evolution rate under air atmosphere from formaldehyde solution over various catalysts at room temperature

Catalyst	Reaction condition	Minimum concentration/ (mol·L^-1)	Optimal or used concentration/ (mol·L^-1)	Optimal H₂ evolution rate/ (mL·g^-1·min^-1)	Ref.
10-Cu/Y₂O₃	0.60 mol/L HCHO; 50 mg catalyst	0.050	0.25	39.8	This work
Nano Cu	0.48 mol/L HCHO; 10 mg catalyst	0.25	1.0	29.5	[14]
Nano Cu	0.50 mol/L HCHO; 20 mg catalyst		1.0	9.6	[15]
Hollow Pd nanotube	0.48 mol/L HCHO; 10 mg catalyst	0.25	1.0	168.0	[9]
Rh nanotube	0.50 mol/L HCHO; 5 mg catalyst		1.0	275.0	[25]
Nano Au	0.50 mol/L HCHO; 10 mg catalyst		1.0	29.5	[26]
Au nanotube	0.50 mol/L HCHO; 10 mg catalyst		1.0	154.0	[27]
Nano Ag	0.50 mol/L HCHO; 10 mg catalyst	0.25	0.50	164.0	[10]
Ag/γ-Al₂O₃	0.87 mol/L HCHO; 50 mg catalyst	>0.10	2.0	415.0	[12]
AgPd₄@C-72	0.26 mol/L HCHO; 15 mg catalyst	0.50	1.0	237.0	[28]
Pd/TiO₂	0.60 mol/L HCHO; 15 mg catalyst	0.25	1.0	250.0	[29]

Fig.8 Time curves of 10-Cu/Y2O3(a) and nano Cu(b) for H2 production from formaldehyde solution(A) and reusability of 10-Cu/Y2O3 for H2 production from formaldehyde solutionReaction conditions are the same as those in Fig.5(A) except the reaction time. (B) Reaction conditions: 0.50 mol/L NaOH; 0.60 mol/L of HCHO; 100 mg 10-Cu/Y2O3, N2 atmosphere.

Fig.9 Schematic illustrations of the catalytic hydrogen production from formaldehyde over x-Cu/Y2O3

Fig.10 XRD patterns of nano Cu(A) and 10-Cu/Y2O3(B) before(a) and after(b) the reaction under N2 atmosphere

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Y₂O₃负载金属Cu在催化甲醛水溶液制氢反应中的Y₂O₃载体效应

Effect of Y₂O₃ Supporter on the Catalytic Hydrogen Production from an Aqueous Formaldehyde Solution Catalyzed by Metal Cu Loaded on Y₂O₃^†

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