生物质衍生Fe-N-C多孔炭材料的制备及其对硝基苯的催化还原性能

doi:10.3969/j.issn.0253-2417.2022.02.009

Abstract

Abstract:

Fir sawdust, urea and FeCl₃·6H₂O were mixed thoroughly at a mass ratio of 1∶[KG-*9]1∶[KG-*9]2 to generate the nitrogen doped porous carbon materials loaded with iron(Fe-N-C) after annealing the mixtures at the temperature of 700-1 000 ℃. The elemental composition, structure and surface properties of the obtained carbon materials at different temperatures were analyzed. Following that, the catalytic performance of the reduction of nitrobenzene were investigated. The results showed that the carbonization temperature had a significant effect on the iron and doped nitrogen species. At 700 ℃, the iron species in Fe-N-C-700 were mainly Fe₃O₄, whereas the nitrogen species were mainly pyridinic-N and pyrrolic-N. As the temperature rose, the iron species became mostly metallic iron, and a portion of the pyridinic-N was changed to graphitic-N. When the temperature was 900 ℃, the manufactured porous carbon material(Fe-N-C-900) had a Fe content of 43.42% and a N content of 2.19%, of which the graphitic-N was 37.7%, pyridinic-N was 23.8%, pyrrolic-N was 22.9% and oxidized-N was 15.6%. When the reaction duration was 2.5 h at 55 ℃. The conversion and selectivity of catalytic reduction of nitrobenzene were close to 100%.The high catalytic performance of Fe-N-C-900 might be due to the synergistic effect between the high content of iron species and graphite nitrogen formed during the calcination process. When Fe-N-C-900 was used for catalytic reduction of nitroarenes with electron-donating substituents such as methyl, amino or hydroxyl group, the corresponding products might be produced with high conversion and selectivity. In additon, when the nitroarenes contained electron-withdrawing substituents such as chlorine or iodine group, the reaction time must be extended to 4 h, and the conversion rate could reach up to 97.3% with the product selectivity above 99%. It indicated that Fe-C-N-900 had good universality for various substrates. And the catalyst had good stability and magnetic recyclability. After 5 times of recycling, the catalytic performance did not decrease obviously, the nitrobenzene conversion remained at 98.3% with the selectivity of 96.5%.

Key words: fir sawdust, porous carbon materials, doping, catalyst

CLC Number:

TQ35

Xing LIU, Zhu YIN, Beili LU, Fengzhen WU, Biao HUANG. Preparation of Biomass-derived Fe-N-C Porous Carbon Material and Its Catalytic Reduction of Nitrobenzene[J]. Chemistry and Industry of Forest Products, 2022, 42(2): 63-70.

Figures/Tables 10

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References 25

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样品 sample	炭化温度/℃ carbonization temp.	C/%	N/%	O/%	Fe/%
Fe-N-C-700	700	31.00	2.75	18.15	33.37
Fe-N-C-800	800	38.42	2.13	11.21	40.88
Fe-N-C-900	900	41.15	2.19	6.50	43.42
Fe-N-C-1000	1000	44.95	0.16	6.43	43.80

样品 sample	吡啶氮/% pyridinic-N	吡咯氮/% pyrrolic-N	石墨氮/% graphitic-N	氧化氮/% oxidized-N
Fe-N-C-700	40.6	30.4	20.7	8.3
Fe-N-C-800	17.7	29.2	27.3	25.8
Fe-N-C-900	23.8	22.9	37.7	15.6
Fe-N-C-1000	15.4	28.4	36.9	19.3

样品 sample	S_BET/(m²·g^-1)	平均孔径/nm average pore size	V_tot/ (cm³·g^-1)	V_mes/ (cm³·g^-1)	V_mic/ (cm³·g^-1)	微孔率/% micropore rate
Fe-N-C-700	295	2.13	0.157	0.031	0.126	80.3
Fe-N-C-800	529	2.54	0.337	0.126	0.211	62.6
Fe-N-C-900	483	2.27	0.274	0.082	0.192	70.0
Fe-N-C-1000	512	2.18	0.280	0.099	0.181	64.6

序号 No.	催化剂 catalyst	温度/℃ temperature	时间/h time	转化率/% conversion rate	选择性/% selectivity
1	Fe-N-C-700	55	2.5	68.1	>99
2	Fe-N-C-800	55	2.5	87.1	>99
3	Fe-N-C-900	55	2.5	99.9	>99
4	Fe-N-C-1000	55	2.5	86.3	>99
5	C-900	55	2.5	4.8	>99
6	N-C-900	55	2.5	2.9	>99
7	Fe-C-900	55	2.5	5.8	>99
8	Fe-N-C-900	25	2.5	32.8	>99
9	Fe-N-C-900	35	2.5	68.9	>99

序号 No.	底物 substrate	产物 product	时间/h time	转化率/% conversion rate	选择性/% selectivity
1	对硝基甲苯1-methyl-4-nitro-benzene	对氨基甲苯p-tolylamine	2.5	>99.0	>99
2	3-硝基邻二甲苯1, 2-dimethyl-3-nitro-benzene	3-氨基邻二甲苯1, 2-dimethyl-3-phenylamine	2.5	>99.0	>99
3	4-硝基苯胺4-nitro-phenylamine	4-氨基苯胺4-nitro-phenylamine	2.5	>99.0	>99
4	4-硝基苯酚4-nitro-phenol	4-氨基苯酚4-amino-phenol	2.5	97.5	>99
5	4-硝基氯苯1-chloro-4-nitro-benzene	4-氨基氯苯4-chloro-phenylamine	2.5	63.2	>99
5	4-硝基氯苯1-chloro-4-nitro-benzene	4-氨基氯苯4-chloro-phenylamine	4	97.3	>99
6	4-硝基碘苯1-iodo-4-nitro-benzene	4-氨基碘苯4-iodo-phenylamine	2.5	60.8	>99
6	4-硝基碘苯1-iodo-4-nitro-benzene	4-氨基碘苯4-iodo-phenylamine	4	98.5	>99

Preparation of Biomass-derived Fe-N-C Porous Carbon Material and Its Catalytic Reduction of Nitrobenzene

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