γ-Mo<sub>2</sub>N/C催化剂的合成及其甲酸脱氢性能研究

路军; 王美君; 王志青; 董立波; 余钟亮; 常丽萍

doi:10.19906/j.cnki.JFCT.2023063

γ-Mo₂N/C催化剂的合成及其甲酸脱氢性能研究

doi: 10.19906/j.cnki.JFCT.2023063

路军^{1, 2, 3,},
王美君^{1, 2, ,},
王志青^3,,
董立波^3,,
余钟亮^4,,
常丽萍^{1, 2,}

1.
太原理工大学省部共建煤基能源清洁高效利用国家重点实验室, 山西太原 030024
2.
太原理工大学煤科学与技术教育部重点实验室, 山西太原 030024
3.
中国科学院山西煤炭化学研究所煤炭转化国家重点实验室, 山西太原 030024
4.
上饶师范大学化学与环境科学学院, 江西上饶 334001

详细信息

通讯作者:
E-mail address: wangmeijun@tyut.edu.cn

中图分类号: TQ116.2
计量
- 文章访问数: 15
- HTML全文浏览量: 31
- PDF下载量: 3
- 被引次数: 0
出版历程
- 收稿日期: 2023-03-02
- 修回日期: 2023-04-09
- 录用日期: 2023-04-10
- 网络出版日期: 2023-09-18

Synthesis of γ-Mo₂N/C catalysts and its performance on formic acid dehydrogenation

LU Jun^{1, 2, 3
,},
WANG Meijun^{1, 2
, ,},
WANG Zhiqing^3
,,
DONG Libo^3
,,
YU Zhongliang^4
,,
CHANG Liping^{1, 2
,}

1.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024 Shanxi, China
2.
Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education, Taiyuan 030024 Shanxi, China
3.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 Shanxi, China
4.
School of Chemistry and Environmental Science, Shangrao Normal University, Shangrao 334001 Jiangxi, China

摘要

摘要: 甲酸 (FA) 因其H含量较高 (4.4%)、易产H₂、可经小平台化合物合成等优势受到广泛关注，而γ-Mo₂N/C对FA沿H₂和CO₂路径分解具有非常高的选择性，产生CO极少，显示出较高的应用价值。基于此，本研究采用对苯二胺和钼酸铵水溶液经前驱体制备γ-Mo₂N/C催化剂，并对其FA分解性能进行了原位评价，采用热重分析 (TG)、X射线衍射 (XRD)、傅里叶变换红外光谱 (FT-IR)、扫描电镜 (SEM)、透射电镜 (TEM) 等表征手段对催化剂的结构和表面官能团进行了分析，利用DFT对FA在γ-Mo₂N (200) 晶面的吸附构型进行了计算，在此基础上，对催化剂性能及FA在其表面的分解机理进行了研究。结果表明，γ-Mo₂N/C在较低温度下即可表现出极高的催化活性，提高γ-Mo₂N在C载体上的分散性能有效改善FA转化率。对苯二胺与钼酸铵的物质的量比为4∶1时，催化性能最佳，在160 ℃、100 h的FA分解实验中，催化剂性能稳定、H₂选择性高(N₂ 40 ml/min, CO < 5.0×10⁻⁵)。而DFT计算表明，FA中O−H键的H原子与γ-Mo₂N/C (200) 晶面上N原子结合的可能性更大，而C=O键的O原子更有可能与γ-Mo₂N/C (200) 晶面上Mo原子结合。上述结果有助于明确FA在γ-Mo₂N/C作用下的分解机理，也显示出非贵金属催化剂γ-Mo₂N/C在FA分解制H₂方面潜在的应用前景。
- 煤基衍生物利用 /
- 甲酸制氢 /
- γ-Mo₂N /
- 负载型催化剂 /
- 氢能
Abstract: Formic acid (FA) has received much attention due to its high hydrogen content (4.4%), easy H₂ production and synthesis from small platform compounds. γ-Mo₂N/C is very selective for the decomposition of FA along the H₂ and CO₂ pathways, generating very little CO and showing high application value. In this study, γ-Mo₂N/C catalysts were prepared using aqueous p-phenylenediamine and ammonium molybdate solutions as precursors, and their FA decomposition performance was evaluated in situ. The adsorption conformation of FA on the crystalline surface of γ-Mo₂N (200) was calculated by DFT, and on this basis, the catalyst performance and the decomposition mechanism of FA on its surface were investigated. The results showed that γ-Mo₂N/C exhibited very high catalytic activity at low temperatures and that improving the dispersion of γ-Mo₂N on the C carrier was effective in improving the FA conversion. The best catalytic performance was achieved at a molar ratio of 4∶1 between p-phenylenediamine and ammonium molybdate, and the catalyst showed stable performance and high H₂ selectivity (N₂ 40 mL/min, CO < 5.0×10⁻⁵) in the FA decomposition experiments at 160 ℃ and 100 h. DFT calculations showed that the H atom of the O−H bond in FA was more likely to bind to the N atom on the crystalline surface of γ-Mo₂N/C (200), while the O atom of the C=O bond are more likely to bind to Mo atoms on the γ-Mo₂N/C (200) crystal plane. The above results help to clarify the mechanism of FA decomposition under the action of γ-Mo₂N/C and show the potential application of the non-precious metal catalyst γ-Mo₂N/C in the decomposition of FA for H₂ production.
- coal-based derivatives utilization /
- hydrogen production from formic acid /
- γ-Mo₂N /
- loaded catalyst /
- hydrogen energy

HTML全文

图 2 反应器示意图

Figure 2 Schematic diagram of the reactor

下载: 全尺寸图片幻灯片

图 3 γ-Mo₂N/C前驱体的TG曲线

Figure 3 TG result of γ-Mo₂N/C precursor; (a) Mass loss ration and DTG curves during γ-Mo₂N/C pyrolysis at 700 ℃; (b) Transformation ratio of γ-Mo₂N/C at different temperatures

下载: 全尺寸图片幻灯片

图 4 高温合成后γ-Mo₂N/C形貌

Figure 4 γ-Mo₂N/C morphology after high temperature synthesis

下载: 全尺寸图片幻灯片

图 5 不同γ-Mo₂N/C的XRD谱图

Figure 5 The XRD results of different γ-Mo₂N/C; (a) XRD patterns of γ-Mo₂N/C synthesised by pyrolysis at different temperatures; (b) XRD patterns of C carriers synthesized at 700 ℃ and different ratios of γ-Mo₂N/C after reaction with formic acid; (c) XRD patterns of C carriers and different ratios of γ-Mo₂N/C at 700 ℃ after passivation with oxygen

下载: 全尺寸图片幻灯片

图 6 700 ℃ 不同对苯二胺与钼酸铵比例合成的γ-Mo₂N/C的XRD谱图

Figure 6 The XRD results of γ-Mo₂N/C synthesized at 700 ℃ with different ratios of p-phenylenediamine to ammonium molybdate

下载: 全尺寸图片幻灯片

图 7 700 ℃合成不同比例催化剂的N₂ 吸附和解吸等温线 (a) 和孔径分布 (b)

Figure 7 N₂ adsorption and desorption isotherms (a) and pore size distribution (b) for the synthesis of different ratios of catalysts at 700 ℃

下载: 全尺寸图片幻灯片

图 8 700 ℃合成不同比例催化剂的扫描电镜照片

Figure 8 Scanning electron microscope images of different scales of catalysts synthesised at 700 ℃

下载: 全尺寸图片幻灯片

图 9 700 ℃合成不同比例催化剂的透射电镜照片

Figure 9 Transmission electron microscopy images of different scales of catalysts synthesised at 700 ℃

下载: 全尺寸图片幻灯片

图 10 催化剂表面的红外光谱谱图

Figure 10 FFIR spectra of the catalyst surface

下载: 全尺寸图片幻灯片

图 11 700 ℃ NM-4∶1的高分辨XPS谱图

Figure 11 High-resolution XPS spectra of NM-4∶1 at 700 ℃; (a) Survey; (b) C 1s; (c) Mo 3d; (d) N 1s

下载: 全尺寸图片幻灯片

图 12 催化剂200晶体表面上FA的吸附状态

Figure 12 Adsorption state of FA on the surface of Catalyst 200 crystals; (a) main view; (b) side view; (c) top view

下载: 全尺寸图片幻灯片

图 13 700 ℃下不同合成比例的γ-Mo₂N/C在不同温度下分解FA的H₂选择性和FA转化率及C载体的FA转化率与其XRD谱图

Figure 13 H₂ selectivity and FA conversion of different synthetic ratios on γ-Mo₂N/C at 700 ℃ for the decomposition of FA at different temperatures and FA conversion of C carriers with their XRD patterns; (a) FA conversion on γ-Mo₂N/C; (b) H₂ selectivity; (c) FA conversion over C carriers; (d) XRD spectra of C carriers

下载: 全尺寸图片幻灯片

图 1 不同温度下FA的两种分解路线ΔG

Figure 1 Two decomposition routes ΔG of FA at different temperatures

下载: 全尺寸图片幻灯片

图 14 (a) 700 ℃ NM-4∶1在160 ℃分解FA的稳定性测试; (b)测试后的XRD谱图

Figure 14 (a) Stability test of NM-4∶1 at 700 ℃ for decomposition of FA at 160 ℃; (b) XRD pattern after the test

下载: 全尺寸图片幻灯片

表 1 不同温度下获得的γ-Mo₂N/C的N和H含量

Table 1 N and H contents of γ-Mo₂N/C obtained at different temperatures

Pyrolysis temperature/℃	N w/%	H w/%
500	14.92	1.80
550	12.45	1.50
600	10.07	1.35
650	7.52	0.92
700	5.75	0.65
750	2.76	0.58
800	2.54	0.44

下载: 导出CSV

表 3 700 ℃下不同比例催化剂Mo质量分数

Table 3 Mo content of different ratios of catalysts at 700 ℃

Sample	Mo (SEM-EDS,%)	Mo (ICP-MS,%)	Mo^{δ +} (XPS,atomic%)
NM-1∶1	47.52	68.16	0.64
NM-2∶1	39.02	59.21	0.38
NM-3∶1	21.44	46.48	0.22
NM-4∶1	15.56	35.80	0.15
NM-5∶1	14.36	33.20	0.07

下载: 导出CSV

表 2 不同合成比例下FA评价后与钝化后获得的γ-Mo₂N/C的N和C质量分数

Table 2 N and C contents of γ-Mo₂N/C obtained after formic acid reaction and passivation at different synthesis ratios

Composite ration	N w/%	C w/%
NM-1∶1^re	1.25	27.94
NM-1∶1^pa	1.28	28.27
NM-2∶1^re	1.86	42.42
NM-2∶1 ^pa	2.14	40.48
NM-3∶1^re	2.28	46.37
NM-3∶1 ^pa	2.34	46.16
NM-4∶1^re	2.53	54.38
NM-4∶1^pa	2.77	52.86
NM-5∶1^re	2.98	55.52
NM-5∶1^pa	3.01	53.70
^re: evaluation of the catalyst after testing; ^pa: passivated catalyst

下载: 导出CSV

表 4 700 ℃合成不同比例催化剂的物理性质

Table 4 Physical properties of catalysts for the synthesis of different ratios of catalysts at 700 ℃

Sample	Surface area/(m²·g⁻¹)	Pore volume/(cm³·g⁻¹)	Macropore ratio/%
NM-1∶1	6.52	0.07	43.28
NM-2∶1	13.44	0.13	52.44
NM-3∶1	13.97	0.15	53.08
NM-4∶1	17.06	0.20	59.20
NM-5∶1	13.88	0.16	46.86

下载: 导出CSV

表 5 700 ℃下不同比例催化剂Mo的质量分数

Table 5 Mo content of different ratios of catalysts at 700 ℃

Sample	Mo (SEM-EDS/%)	Mo (ICP-MS/%)	Mo^{δ +} (XPS,atomic/%)
NM-1∶1	47.52	68.16	0.64
NM-2∶1	39.02	59.21	0.38
NM-3∶1	21.44	46.48	0.22
NM-4∶1	15.56	35.80	0.15
NM-5∶1	28.24	35.83	0.31

下载: 导出CSV

表 6 钝化和评价后的γ-Mo₂N/C的元素分析

Table 6 Elemental content of γ-Mo₂N/C after passivation and evaluation

Sample	Element abundance w/%
Sample	N	C	H
Fresh	2.54	53.70	0.77
Long term	2.78	55.55	0.76

下载: 导出CSV

表 7 钝化和评价后的γ-Mo₂N/C的物理特性

Table 7 Physical properties of γ-Mo₂N/C after passivation and evaluation

Sample	Surface area/(m²·g⁻¹)	Pore volume/(cm³·g⁻¹)	Macropore ratio/%
Fresh	17.06	0.20	59.20
Long term	16.24	0.11	58.00

下载: 导出CSV

参考文献(32)

[1]	STAFFELL I, SCAMMAN D, ABAD A V, et al. The role of hydrogen and fuel cells in the global energy system[J]. Energ Environ Sci,2019,12(2):463−491. doi: 10.1039/C8EE01157E
[2]	LEBROUHI B E, DJOUPO J J, LAMRANI B, et al. Global hydrogen development a technological and geopolitical overview[J]. Int J Hydrog Energy,2022,47(11):7016−7048. doi: 10.1016/j.ijhydene.2021.12.076
[3]	ZHANG F, ZHAO P C, NIU M, et al. The survey of key technologies in hydrogen energy storage[J]. Int J Hydrog Energy,2016,41(33):14535−14552. doi: 10.1016/j.ijhydene.2016.05.293
[4]	PREUSTER P, PAPP C, WASSERSCHEID P. Liquid organic hydrogen carriers (LOHCs): Toward a hydrogen free hydrogen economy[J]. Acc Chem Res,2017,50(1):74−85. doi: 10.1021/acs.accounts.6b00474
[5]	SINGH A K, SINGH S, KUMAR A. Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system[J]. Catal Sci Technol,2016,6(1):12−40. doi: 10.1039/C5CY01276G
[6]	PREUSTER P, ALBERT J. Biogenic formic acid as a green hydrogen carrier[J]. Energy Technol,2018,6(3):501−509. doi: 10.1002/ente.201700572
[7]	LANG C G, JIA Y, YAO X D. Recent advances in liquid-phase chemical hydrogen storage[J]. Energy Storage Mater,2020,26:290−312. doi: 10.1016/j.ensm.2020.01.010
[8]	BULUSHEV D A, ROSS J R H. Heterogeneous catalysts for hydrogenation of CO₂ and bicarbonates to formic acid and formates[J]. Catal Rev-Sci Eng,2018,60(4):566−593. doi: 10.1080/01614940.2018.1476806
[9]	BULUSHEV D A, ROSS J R H. Towards sustainable production of formic acid[J]. ChemSusChem,2018,11(5):821−836. doi: 10.1002/cssc.201702075
[10]	NEMATOLLAHI P, MA H Y, SCHNEIDER W F, et al. DFT and microkinetic comparison of Ru-doped porphyrin-like graphene and nanotubes toward catalytic formic acid decomposition and formation[J]. J Phys Chem C,2021,125(34):18673−18683. doi: 10.1021/acs.jpcc.1c03914
[11]	LI Y S, HE Y L, YANG W W. A high-performance direct formate-peroxide fuel cell with palladium gold alloy coated foam electrodes[J]. J Power Sources,2015,278:569−573. doi: 10.1016/j.jpowsour.2014.12.064
[12]	YU X W, MANTHIRAM A. Catalyst selective, scalable membraneless alkaline direct formate fuel cells[J]. Appl Catal B-Environ,2015,165:63−67. doi: 10.1016/j.apcatb.2014.09.069
[13]	COPENHAVER T S, PUROHIT K H, DOMALAON K, et al. A microfluidic direct formate fuel cell on paper[J]. Electrophoresis,2015,36(16):1825−1829. doi: 10.1002/elps.201400554
[14]	VO T, PUROHIT K, NGUYEN C, et al. Formate: an energy storage and transport bridge between carbon dioxide and a formate fuel cell in a single device[J]. ChemSusChem,2015,8(22):3853−3858. doi: 10.1002/cssc.201500958
[15]	LI J J, CHEN W, ZHAO H, et al. Size-dependent catalytic activity over carbon-supported palladium nanoparticles in dehydrogenation of formic acid[J]. J Catal,2017,352:371−381. doi: 10.1016/j.jcat.2017.06.007
[16]	MONTANDON-CLERC M, DALEBROOK A F, LAURENCZY G. Quantitative aqueous phase formic acid dehydrogenation using iron(II) based catalysts[J]. J Catal,2016,343:62−67. doi: 10.1016/j.jcat.2015.11.012
[17]	CHEN H L, JIANG D C, SUN Z J, et al. Cobalt nitride as an efficient cocatalyst on CdS nanorods for enhanced photocatalytic hydrogen production in water[J]. Catal Sci Technol,2017,7(7):1515−1522. doi: 10.1039/C7CY00046D
[18]	SUN Z, CHEN H, ZHANG L, et al. Enhanced photocatalytic H₂ production on cadmium sulfide photocatalysts using nickel nitride as a novel cocatalyst[J]. J Mater Chem A,2016,4(34):13289−13295. doi: 10.1039/C6TA04696G
[19]	DHANASEKARAN P, SALUNKE H G, GUPTA N M. Visible-light-induced photosplitting of water over γ′-Fe₄N and γ′-Fe₄N/α-Fe₂O₃ Nanocatalysts[J]. J Phys Chem C,2012,116(22):12156−12164. doi: 10.1021/jp303255f
[20]	MENG X J, QI W L, KUANG W D, et al. Chromium-titanium nitride as an efficient co-catalyst for photocatalytic hydrogen production[J]. J Mater Chem A,2020,8(31):15774−15781. doi: 10.1039/D0TA00488J
[21]	TOMINAGA H, NAGAI M. Reaction mechanism for hydrodenitrogenation of carbazole on molybdenum nitride based on DFT study[J]. Appl Catal A-Gen,2010,389(1-2):195−204. doi: 10.1016/j.apcata.2010.09.020
[22]	GHAMPSON I T, SEPULVEDA C, GARCIA R, et al. Hydrodeoxygenation of guaiacol over carbon-supported molybdenum nitride catalysts: Effects of nitriding methods and support properties[J]. Appl Catal A-Gen,2012,439-440:111−124. doi: 10.1016/j.apcata.2012.06.047
[23]	SONG Y J, YUAN Z Y. One-pot synthesis of Mo₂N/NC catalysts with enhanced electrocatalytic activity for hydrogen evolution reaction[J]. Electrochim Acta,2017,246:536−543. doi: 10.1016/j.electacta.2017.06.086
[24]	YU Z L, AN X W, KURNIA I, et al. Full spectrum decomposition of formic acid over γ-Mo₂N-based catalysts: From dehydration to dehydrogenation[J]. ACS Catal,2020,10(9):5353−5361. doi: 10.1021/acscatal.0c00752
[25]	KANAZAWA S, YAMADA Y, SATO S. Infrared spectroscopy of graphene nanoribbons and aromatic compounds with sp³C−H (methyl or methylene groups)[J]. J Mater Sci,2021,56(21):12285−12314. doi: 10.1007/s10853-021-06001-1
[26]	LIN H, LONG J, GU Q, et al. In situ IR study of surface hydroxyl species of dehydrated TiO₂: Towards understanding pivotal surface processes of TiO₂ photocatalytic oxidation of toluene[J]. Phys Chem Chem Phys,2012,14(26):9468−9474. doi: 10.1039/c2cp40893g
[27]	CHEN T, WU G P, FENG Z C, et al. In situ FT-IR study of photocatalytic decomposition of formic acid to hydrogen on Pt/TiO₂ catalyst[J]. Chin J Catal,2008,29(2):105−107. doi: 10.1016/S1872-2067(08)60019-4
[28]	LV Z, TAHIR M, LANG X W, et al. Well dispersed molybdenum nitrides on a nitrogen-doped carbon matrix for highly efficient hydrogen evolution in alkaline media[J]. J Mater Chem A,2017,5(39):20932−20937. doi: 10.1039/C7TA06981B
[29]	GANIYU S A, ALHOOSHANI K, ALI S A. Single pot synthesis of Ti-SBA-15-NiMo hydrodesulfurization catalysts: Role of calcination temperature on dispersion and activity[J]. Appl Catal B-Environ,2017,203:428−441. doi: 10.1016/j.apcatb.2016.10.052
[30]	TRILLO J M, MUNUERA G, CRIADO J M. Catalytic decomposition of formic acid on metal oxides[J]. Catal Rev-Sci Eng,2006,7(1):51−86.
[31]	POPOVA G Y, CHESALOV Y A, SADOVSKAYA E M, et al. Effect of water on decomposition of formic acid over V-Ti oxide catalyst: Kinetic and in situ FTIR study[J]. J Mol Catal a-Chem,2012,357:148−153. doi: 10.1016/j.molcata.2012.02.005
[32]	SADOVSKAYA E M, CHESALOV Y A, GONCHAROV V B, et al. Formic acid decomposition over V-Ti oxide catalyst: Mechanism and kinetics[J]. Mol Catal,2017,430:54−62. doi: 10.1016/j.molcata.2016.12.010