Rh/g-C<sub>3</sub>N<sub>4</sub>纳米催化剂催化水合肼分解制氢性能研究

邱小魁; 孙佳丽; 花俊峰; 郑君宁; 万超; 许立信

doi:10.19906/j.cnki.JFCT.2022093

Rh/g-C₃N₄纳米催化剂催化水合肼分解制氢性能研究

doi: 10.19906/j.cnki.JFCT.2022093

邱小魁^1,,
孙佳丽^1,,
花俊峰^2,,
郑君宁^3,,
万超^{1, 3, 4, 5,},
许立信^{1, 3, ,}

1.
安徽硅宝有机硅新材料有限公司, 安徽马鞍山 243000
2.
浙江省环境科技有限公司, 浙江杭州 310027
3.
安徽工业大学化学与化工学院, 安徽马鞍山 243000
4.
浙江大学化学工程与生物工程学院, 浙江杭州 310027
5.
南开大学先进能源材料化学教育部重点实验室, 天津 300071

基金项目: 国家自然科学基金青年基金（22108238, U22A20408），安徽省自然科学基金青年基金（1908085QB68），安徽省科技重大专项（201903a05020055），中国博士后面上项目(2019M662060)和特别资助站中项目(2020T130580, PC2022046)资助

详细信息

通讯作者:
E-mail: lxxu@hotmail.com

中图分类号: O643.36
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出版历程
- 收稿日期: 2022-09-23
- 修回日期: 2022-12-13
- 录用日期: 2022-12-13
- 网络出版日期: 2022-12-26
- 刊出日期: 2023-09-30

Hydrogen generation from hydrous hydrazine over Rh/g-C₃N₄ nanocatalysts

QIU Xiao-kui^1
,,
SUN Jia-li^1
,,
HUA Jun-feng^2
,,
ZHENG Jun-ning^3
,,
WAN Chao^{1, 3, 4, 5
,},
XU Li-xin^{1, 3
, ,}

1.
GBXF Silicones Co., Ltd, Ma’anshan 243000, China
2.
Zhejiang Environment Technology Co., Ltd, Hangzhou 310027, China
3.
School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma’anshan 243000, China
4.
College of Chemical Engineering and Biological Engineering, Zhejiang University, Hangzhou 310027, China
5.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China

Funds: The project was supported by the National Natural Science Foundation of China (22108238, U22A20408), Anhui Provincial Natural Science Foundation (1908085QB68), Major Science and Technology Project of Anhui Province (201903a05020055) and China Postdoctoral Science Foundation (2019M662060, 2020T130580,PC2022046)

摘要

摘要: 本研究将三聚氰胺在静态空气中焙烧合成的g-C₃N₄作为载体，通过简单的浸渍还原法将Rh纳米粒子负载在g-C₃N₄载体上制备出Rh/g-C₃N₄催化剂。采用多种表征方法对催化剂的微观结构、组成成分进行研究。此外，还研究了反应温度和NaOH浓度对催化剂催化水合肼分解的影响。研究结果表明，催化剂优异的催化活性源于g-C₃N₄载体为金属Rh提供了锚定位点，并且载体和金属之间存在强相互作用。催化剂的催化活性随着反应温度的升高而不断提升，当NaOH浓度为0.75 mol/L时Rh/g-C₃N₄催化剂具有最高的催化活性。Rh/g-C₃N₄催化剂催化水合肼分解制氢的活化能为30.7 kJ/mol，TOF值为1466.4 h⁻¹，在经过五次循环后，催化剂依旧保持着较好的催化活性，表明催化剂具有良好的循环稳定性。
- 水合肼 /
- g-C₃N₄ /
- Rh /
- 分解制氢
Abstract: In this paper, g-C₃N₄ obtained by calcining melamine at high temperature in static air was used as the carrier, and the precious metal Rh was used as the active component. The Rh nanoparticles were supported on the g-C₃N₄ support by a simple impregnation reduction method to prepare high activity and high selectivity. Various characterization methods were used to study the microstructure and composition of the catalyst. In addition, the effect of reaction temperature and NaOH concentration on the catalytic decomposition of hydrous hydrazine was also investigated. The results show that the excellent catalytic activity of the catalyst stems from the fact that the g-C₃N₄ support provides anchor sites for the metal Rh and the support and the strong metal-support interactions. The catalytic activity of the catalyst increases with the increase of the reaction temperature, and the Rh/g-C₃N₄ catalyst has the highest catalytic activity when the NaOH concentration is 0.75 mol/L. The Rh/g-C₃N₄ catalyst has an activation energy of 30.7 kJ/mol and TOF value of 1466.4 h⁻¹ for catalyzing the decomposition of hydrous hydrazine for hydrogen production. After 5 cycles, the catalyst still maintains a good catalytic activity, indicating that the catalyst has a good cyclic stability.
- hydrous hydrazine /
- g-C₃N₄ /
- rhodium /
- dehydrogenation

HTML全文

FIG. 2675. FIG. 2675.

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图 1 Rh/g-C₃N₄合成示意图

Figure 1 Synthetic schematic illustration of Rh/g-C₃N₄

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图 2 不同放大倍数下Rh/g-C₃N₄催化剂的TEM照片

Figure 2 TEM images of Rh/g-C₃N₄ with different magnification

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图 3 Rh/g-C₃N₄催化剂的XRD谱图

Figure 3 X-ray diffraction (XRD) patterns of Rh/g-C₃N₄

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图 4 (a) Rh/g-C₃N₄的XPS测试全谱图，(b) Rh/g-C₃N₄的Rh 3d区域XPS谱图，Rh/g-C₃N₄和g-C₃N₄的 (c) C 1s区域，(d) N 1s区域XPS谱图

Figure 4 XPS spectra of Rh/g-C₃N₄ sample (a) Full XPS spectrum and (b) Rh 3d, (c) the XPS of C 1s regions and (d) N 1s regions of Rh/g-C₃N₄ and g-C₃N₄

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图 5 (a) 343 K下Rh/g-C₃N₄在不同浓度的碱溶液中催化水合肼分解产生的气体；(b) 343 K下不同NaOH浓度反应对应的TOF值；(c) 不同温度下Rh/g-C₃N₄上水合肼分解生成气体与时间的关系；(d) Rh/g-C₃N₄催化剂催化水合肼分解阿伦尼乌斯曲线

Figure 5 (a) Plots equivalent produced by dehydrogenation of hydrous hydrazine catalyzed by Rh/g-C₃N₄ in alkaline solutions with different concentrations at 343 K; (b) TOF values corresponding to different NaOH concentration reactions at 343 K; (c) Relationship between volume and time of gas generated by hydrous hydrazine dehydrogenation at Rh/g-C₃N₄ at different temperatures; (d) Arrhenius diagram of dehydrogenation of hydrous hydrazine catalyzed by Rh/g-C₃N₄ catalyst

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图 6 Rh/g-C₃N₄催化水合肼分解产氢循前后的XRD谱图

Figure 6 X-ray diffraction (XRD) patterns of Rh/g-C₃N₄ befor and after reaction

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图 7 Rh/g-C₃N₄在343 K下催化水合肼产氢循环测试

Figure 7 Recycling performance of Rh/g-C₃N₄ at 343 K

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表 1 Rh/g-C₃N₄催化剂的ICP-AES测试

Table 1 ICP-AES results of Rh/g-C₃N₄ catalyst

Catalyst	Rh w/%	Final metals/catalyst (mmol·(100 mg)⁻¹)
Rh/g-C₃N₄	12.37	0.137

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表 2 不同催化剂在水合肼产氢中的性能

Table 2 Comparison performance of different catalysts for dehydrogenation of hydrous hydrazine

Catalyst	T/K	TOF/ h⁻¹	E_a/ (kJ·mol⁻¹)	Ref.
Rh/g-C₃N₄	323	1466.4	30.7	This work
Rh₅₅Ni₄₅/Ce(OH)CO₃	323	395	38.8	[19]
Rh₄Ni₁@RGO	298	20.1	−	[24]
Rh₄Ni	298	6	−	[33]
Ni_0.90Pt_0.05Rh_0.05/La₂O₃	298	66.7	−	[34]
Ni₆₆Rh₃₄@ZIF-8	323	140	58.1	[35]
Rh₄₇Ni₁₈P₃₅@MOF-74	323	715.4	49.39	[21]
Ni₃₇Pt₆₃/g-C₃N₄	323	570	36.6	[29]
Ni_0.4Pt_0.6/CNTs	323	1725.3	36.3	[36]
Pt_0.6Ni_0.4/(MnO_x)₂-C₃N₄	323	2749	48.7	[37]

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参考文献(37)

[1]	WAN C, SUN L, XU L, CHENG D G, CHEN F, ZHAN X, YANG Y. Novel NiPt alloy nanoparticle decorated 2D layered g-C₃N₄ nanosheets: a highly efficient catalyst for hydrogen generation from hydrous hydrazine[J]. J Mater Chem A,2019,7(15):8798−8804. doi: 10.1039/C9TA01535C
[2]	LIU M M, ZHOU L, WAN C, YE M F, XU L X. Achieving com-plete hydrogen evolution from N₂H₄BH₃ over mesoporous TiO₂ immobilized NiPt alloy nanoparticles[J]. ChemistrySelect,2021,6(34):9185−9190. doi: 10.1002/slct.202102592
[3]	AKBAYRAK S, TONBUL Y, ÖZKAR S. Magnetically separable Rh⁰/Co₃O₄ nanocatalyst provides over a million turnovers in hydrogen release from ammonia borane[J]. ACS Sustainable Chem Eng,2020,8(10):4216. doi: 10.1021/acssuschemeng.9b07402
[4]	WAN C, ZHOU L, SUN L, XU L X, CHENG D G, CHEN F Q, ZHAN X L, YANG Y R. Boosting visible-light-driven hydrogen evolution from formic acid over AgPd/2D g-C₃N₄ nanosheets Mott-Schottky photocatalyst[J]. Chem Eng J,2020,396:125229. doi: 10.1016/j.cej.2020.125229
[5]	SEMIZ L. Hydrogen generation from ammonia borane by polymer supported platinum films[J]. Chem Phys Lett,2021,767:138365. doi: 10.1016/j.cplett.2021.138365
[6]	DU X, CAI P, LUO W, CHENG G Z. Facile synthesis of P-doped Rh nanoparticles with superior catalytic activity toward dehydrogenation of hydrous hydrazine[J]. Int J Hydrogen Energy,2017,42(9):6137−6143. doi: 10.1016/j.ijhydene.2016.12.049
[7]	任壮禾, 张欣, 高明霞, 潘洪革, 刘永锋. Ti基催化剂改性的NaAlH₄储氢材料研究进展[J]. 稀有金属,2021,45(5):569. REN Zhuang-he, ZHANG Xin, GAO Ming-xia, PAN Hong-ge, LIU Yong-feng. Research progress in Ti-based catalysts-modified NaAlH₄ hydrogen storage materials[J]. Chin J Rare Met,2021,45(5):569.
[8]	路金林, 王琳, 李继东, 王一雍, 李胜利, 崔小强. 电沉积法制备钯金纳米催化剂及其对甲醇催化性能的研究[J]. 稀有金属,2015,39(6):493. doi: 10.13373/j.cnki.cjrm.2015.06.003 LU Jin-lin, WANG Lin, LI Ji-dong, WANG Yi-yong, LI Sheng-li, CUI Xiao-qiang. Pd-Au nano-catalysts synthesized by electrodeposition and its cata-lytic performance for methanol[J]. Chin J Rare Met,2015,39(6):493. doi: 10.13373/j.cnki.cjrm.2015.06.003
[9]	任杨斌, 范燕平, 刘宪云, 段继转, 刘宝忠. 氨硼烷水解制氢贵金属催化剂研究进展[J]. 当代化工研究,2022,3:1. doi: 10.3969/j.issn.1672-8114.2022.05.001 REN Yang-bin, FAN Yan-ping, LIU Xian-yun, DUAN Ji-zhuan, LIU Bao-zhong. Research progress of hydrolytic noble metal catalyst for hydrogen production from ammonia borane[J]. Mod Chem Res,2022,3:1. doi: 10.3969/j.issn.1672-8114.2022.05.001
[10]	WANG Y, SHEN J L, HUANG Y, LIU X, ZHAO Q X, ASTRUC D. Acid‐and base‐catalyzed hydrolytic hydrogen evolution from diboronic acid[J]. Eur J Inorg Chem,2021,29:3013−3018.
[11]	LIU X Y, LIU Y, WANG J C, MA J. Anatase-type TiO₂-modified amorphous NiMo nanoparticles with superior catalytic performance toward dehydrogenation of hydrous hydrazine[J]. Ind Eng Chem Res,2022,61(4):1636−1643. doi: 10.1021/acs.iecr.1c03398
[12]	LI M Y, ZHOU Z Z, HU L, WANG S Y, ZHOU Y Z, ZHU R B, CHU X Z, VINU A, WAN T, GAZORLA G, YI J B, CHU D. W. Hydrazine hydrate intercalated 1T-dominant MoS₂ with superior ambient stability for highly efficient electrocatalytic applications[J]. ACS Appl Mater Interfaces,2022,14(14):16338−16347. doi: 10.1021/acsami.2c02675
[13]	QIU Y P, SHI Q, ZHOU L L, CHEN M H, CHEN C, TANG P P, WALK-ER G S, WANG P. NiPt nanoparticles anchored onto hierarchical nanoporous N-doped carbon as an efficient catalyst for hydrogen generation from hydrazine monohydrate[J]. ACS Appl Mater Interfaces,2020,12(16):18617−18624. doi: 10.1021/acsami.0c03096
[14]	GUO F, ZOU H, YAO Q, HUANG B, LU Z H. Monodispersed bi-metallic nanoparticles anchored on TiO₂-decorated titanium carbide MXene for efficient hydrogen production from hydra-zine in aqueous solution[J]. Renewable Energy,2020,155:1293−1301. doi: 10.1016/j.renene.2020.04.047
[15]	SINGH S K, ZHANG X B, XU Q. Room-temperature hydrogen generation from hydrous hydrazine for chemical hydrogen storage[J]. J Am Chem Soc,2009,131(29):9894−9895. doi: 10.1021/ja903869y
[16]	SHARMA P, SASSON Y. Highly active Ru-g-C₃N₄ photocatalyst for visible light assisted selective hydrogen transfer reaction using hydrazine at room temperature[J]. Catal Commun,2017,102:48−52. doi: 10.1016/j.catcom.2017.08.019
[17]	YAO Q L, HE M, HONG X L, CHEN X Y, FENG G, LU Z H. Hydrogen production via selective dehydrogenation of hydrazine borane and hydrous hydrazine over MoO_x-promoted Rh catalyst[J]. Int J Hydrogen Energy,2019,44(53):28430−28440. doi: 10.1016/j.ijhydene.2019.02.105
[18]	ZHAO P P, CAO N, LUO W, CHENG G Z. Nanoscale MIL-101 supported RhNi nanoparticles: An efficient catalyst for hydro-gen generation from hydrous hydrazine[J]. J Mater Chem A,2015,3(23):12468−12475. doi: 10.1039/C5TA02201K
[19]	CHEN J M, YAO Q L, ZHU J, CHEN X S, LU Z H. Rh-Ni nanopar-ticles immobilized on Ce(OH)CO₃ nanorods as highly efficient catalysts for hydrogen generation from alkaline solution of hydrazine[J]. Int J Hydrogen Energy,2016,41(6):3946−3954. doi: 10.1016/j.ijhydene.2015.12.158
[20]	YANG P, YANG L J, GAO Q, LUO Q, ZHAO X C, MAI X M, FU Q L, DONG M Y, WANG J C, HAO Y W, YANG R Z, LAI X C, WU S D, SHAO Q, DING T, LIN J, GUO Z H. Anchoring carbon nanotubes and post-hydroxylation treatment enhanced Ni nanofiber catalysts towards efficient hydrous hydrazine decomposition for effective hydrogen generation[J]. Chem Commun,2019,55(61):9011−9014. doi: 10.1039/C9CC04559G
[21]	JIANG R, QU X, ZENG F, LI Q, ZHENG X, XU Z, PENG J. MOF-74-immobilized ternary RhNiP nanoparticles as highly efficient hydrous hydrazine dehydrogenation catalysts in alkaline solutions[J]. Int J Hydrogen Energy,2019,44(13):6383−6391. doi: 10.1016/j.ijhydene.2019.01.117
[22]	WAN C, ZHOU L, XU S M, JIN B Y, GE X, QIAN X, XU L X, CHEN F Q, ZHAN X L, YANG Y R, CHENG D G. Defect engineered mesoporous graphitic carbon nitride modified with AgPd nanoparticles for enhanced photocatalytic hydrogen evolution from formic acid[J]. Chem Eng J,2022,429:132388. doi: 10.1016/j.cej.2021.132388
[23]	DU Y S, SU J, LUO W, CHENG G Z. Graphene-supported nickel-platinum nanoparticles as efficient catalyst for hydrogen generation from hydrous hydrazine at room temperature[J]. ACS Appl Mater Interfaces,2015,7(2):1031−1034. doi: 10.1021/am5068436
[24]	WANG J, ZHANG X B, WANG Z L, WANG L M, ZHANG Y. Rhodiumenickel nanoparticles grown on graphene as highly efficient catalyst for complete decomposition of hydrous hydrazine at room temperature for chemical hydrogen storage[J]. Energy Environ Sci,2012,5:6885−6888. doi: 10.1039/c2ee03344e
[25]	ZOU H T, ZHANG S L, HONG X L, YAO Q L, LUO Y, LU Z H. Immobilization of Ni-Pt nanoparticles on MIL-101/rGO composite for hydrogen evolution from hydrous hydrazine and hydrazine borane[J]. J Alloys Compd,2020,835:155426. doi: 10.1016/j.jallcom.2020.155426
[26]	CAO N, YANG L, DU C, SU J, LUO W, CHENG G Z. Highly efficient dehydrogenation of hydrazine over graphene supported flower-like Ni-Pt nanoclusters at room temperature[J]. J Mater Chem A,2014,2(35):14344−14347. doi: 10.1039/C4TA02964J
[27]	XIA B Q, LIU T, LUO W, CHENG G Z. NiPt-MnO_x supported on N-doped porous carbon derived from metal-organic frameworks for highly efficient hydrogen generation from hydrazine[J]. J Mater Chem A,2016,4(15):5616−5622. doi: 10.1039/C6TA00766J
[28]	XING W N, TU W G, HAN Z H, HU Y D, MENG Q Q, CHEN G. Template-induced high-crystalline g-C₃N₄ nanosheets for enhanced photocatalytic H₂ evolution[J]. ACS Energy Lett,2018,3(3):514−519. doi: 10.1021/acsenergylett.7b01328
[29]	XU L X, LIU N, HONG B, CUI P, CHENG D G, CHEN F Q, AN Y, WAN C. Nickel-platinum nanoparticles immobilized on graphitic carbon nitride as highly efficient catalyst for hydrogen release from hydrous hydrazine[J]. RSC Adv,2016,6(38):31687−31691. doi: 10.1039/C6RA01335J
[30]	ZHANG W, JIAJUNWANG J J, LIU Z W, PI Y B, TAN R. Visible light-driven oxidant-free dehydrogenation of alcohols in water using porous ultrathin g-C₃N₄ nanosheets[J]. Green Energy Environ,2022,7:712−722. doi: 10.1016/j.gee.2020.11.019
[31]	张安琪, 姚淇露, 卢章辉. 水合肼分解产氢催化剂研究进展[J]. 化学学报,2021,79(7):885−902. doi: 10.6023/A21030126 ZHANG An-qi, YAO Qi-lu, LU Zhang-hui. Recent progress on catalysts for hydrogen evolution from decomposition of hydrous hydrazine[J]. Acta Chim Sin,2021,79(7):885−902. doi: 10.6023/A21030126
[32]	SONG F Z, YANG X C, XU Q. Ultrafine bimetallic Pt-Ni nanoparticles achieved by metal-organic framework templated zirconia/porous carbon/reduced graphene oxide: Remarkable catalytic activity in dehydrogenation of hydrous hydrazine[J]. Small Methods,2020,4(1):1900707. doi: 10.1002/smtd.201900707
[33]	SINGH S K, XU Q. Complete conversion of hydrous hydrazine to hydrogen at room temperature for chemical hydrogen storage[J]. J Am Chem Soc,2009,131:18032−18033. doi: 10.1021/ja908037t
[34]	SONG-Il O, YAN J M, WANG H L, WANG Z L, JIANG Q. Ni/La₂O₃ catalyst containing low content platinumerhodium for the dehydrogenation of N₂H₄·H₂O at room temperature[J]. J Power Sources,2014,262:386−390. doi: 10.1016/j.jpowsour.2014.03.059
[35]	XIA B, CAO N, DAI H, SU J, WU X, LUO W, CHENG G Z. Bimetallic nickelerhodium nanoparticles supported on ZIF-8 as highly efficient catalysts for hydrogen generation from hydrazine in alkaline solution[J]. ChemCatChem,2014,6:2549−2552. doi: 10.1002/cctc.201402353
[36]	ZHANG M Y, LIU L, LU S, XU L X, AN Y, WAN C. Facile fabrication of NiPt/CNTs as an efficient catalyst for hydrogen production from hydrous hydrazine[J]. ChemistrySelect,2019,4:10494−10500. doi: 10.1002/slct.201902762
[37]	ZHENG J N, LIANG Y, LI G, JIN B Y, WAN C, YE M F, XU L X. Mn-modified graphitic carbon nitride-supported bimetallic PtNi nanoparticles for hydrogen generation from hydrous hydrazine[J]. ChemistrySelect, 2022, https://doi.org/10.1002/slct.202202690.