Synthesis of p-aminophenol by transfer hydrogenation of nitrobenzene using formic acid as hydrogen source

doi:10.16085/j.issn.1000-6613.2023-1200

Abstract

Abstract:

With UiO-66 as the precursor, ZrO₂@C was prepared by calcination in N₂ atmosphere. Then, Pd/ZrO₂@C was prepared by impregnation method. In this paper, the catalytic transfer hydrogenation of nitrobenzene (NB) to p-aminophenol (PAP) over Pd/ZrO₂@C+SO₄^2-/ZrO₂ was studied with formic acid (FA) as hydrogen source. Characterization results showed that tetragonal ZrO₂ was present in ZrO₂@C and was embedded in amorphous C. With the increase of calcination temperature and time in the air, the C content and specific surface area of ZrO₂@C decreased accordingly, while the Pd particle size became larger. Pd in the Pd/ZrO₂@C catalyst was in the form of Pd⁰ and Pd²⁺. The content of Pd²⁺ decreased with C content, While the content of Pd⁰ increased. When the content of Pd⁰ was higher than that of Pd²⁺, PAP selectivity decreased obviously. Pd/ZrO₂@C-200-4+SO₄^2-/ZrO₂ exhibited good catalytic activity at 140℃ for 6h. The conversion of NB was 63.7% and the selectivity of PAP was 42.3%.

Key words: catalysis, hydrogenation, support, p-aminophenol, formic acid, nitrobenzene

摘要：

以UiO-66为前体，在N₂气氛下焙烧制备了ZrO₂@C，以其为载体，利用浸渍法制备了Pd/ZrO₂@C催化剂。以Pd/ZrO₂@C+SO₄^2-/ZrO₂为催化剂，对以甲酸（FA）为氢源、硝基苯（NB）转移加氢合成对氨基苯酚（PAP）的反应进行了研究。通过表征发现，Pd/ZrO₂@C载体中的ZrO₂为四方相ZrO₂，包埋在无定形C中。随着ZrO₂@C在空气中焙烧温度的升高和焙烧时间的增加，其C含量和比表面积随之下降，同时Pd颗粒尺寸变大。Pd/ZrO₂@C催化剂中Pd以Pd⁰和Pd²⁺两种形式存在，且随着C含量的减少，Pd⁰含量增加，Pd²⁺含量减少；当Pd⁰含量明显高于Pd²⁺，其对PAP的选择性明显下降。在140℃、反应6h的条件下，Pd/ZrO₂@C-200-4+SO₄^2-/ZrO₂具有较好的催化性能，NB转化率为63.7%，PAP选择性为42.3%。

关键词: 催化, 加氢, 载体, 对氨基苯酚, 甲酸, 硝基苯

CLC Number:

TQ246.35

WANG Yufei, JIA Yu, ZHANG Yisheng, XUE Wei, LI Fang, WANG Yanji. Synthesis of p-aminophenol by transfer hydrogenation of nitrobenzene using formic acid as hydrogen source[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4421-4431.

王雨菲, 贾宇, 张议升, 薛伟, 李芳, 王延吉. 甲酸为氢源硝基苯转移加氢合成对氨基苯酚[J]. 化工进展, 2024, 43(8): 4421-4431.

Figures/Tables 15

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样品	C质量分数/%	比表面积 /m²·g^-1	孔容积 /cm³·g^-1	孔径/nm
ZrO₂@C	24.38	240.95	0.23	3.82
ZrO₂@C-200-4	22.74	246.94	0.25	4.01
ZrO₂@C-300-1.5	7.56	206.56	0.20	3.92
ZrO₂@C-300-4	2.77	173.74	0.26	6.02
ZrO₂@C-400-4	0.50	118.44	0.26	8.84

样品	C质量分数/%	比表面积 /m²·g^-1	孔容积 /cm³·g^-1	孔径/nm
ZrO₂@C	24.38	240.95	0.23	3.82
ZrO₂@C-200-4	22.74	246.94	0.25	4.01
ZrO₂@C-300-1.5	7.56	206.56	0.20	3.92
ZrO₂@C-300-4	2.77	173.74	0.26	6.02
ZrO₂@C-400-4	0.50	118.44	0.26	8.84

样品	O 1s/%	Zr 3d/%	O/Zr
ZrO₂@C	30.65	10.88	2.82
ZrO₂@C-200-4	33.67	11.64	2.89
ZrO₂@C-300-1.5	43.74	15.34	2.85
ZrO₂@C-300-4	51.55	18.34	2.81
ZrO₂@C-400-4	59.73	21.97	2.72

样品	O 1s/%	Zr 3d/%	O/Zr
ZrO₂@C	30.65	10.88	2.82
ZrO₂@C-200-4	33.67	11.64	2.89
ZrO₂@C-300-1.5	43.74	15.34	2.85
ZrO₂@C-300-4	51.55	18.34	2.81
ZrO₂@C-400-4	59.73	21.97	2.72

样品	比表面积/m²·g^-1	孔容积/cm³·g^-1	孔径/nm
Pd/ZrO₂@C	234.37	0.26	4.51
Pd/ZrO₂@C-200-4	223.02	0.29	5.15
Pd/ZrO₂@C-300-1.5	168.93	0.24	5.62
Pd/ZrO₂@C-300-4	160.99	0.21	5.10
Pd/ZrO₂@C-400-4	115.89	0.25	8.69