Multi-site Co<sub>2</sub>P catalyst derived from soybean biomass for dehydrogenation of formic acid

WANG Bixi; LIU Zeyu; WU Yabei; YANG Yanyan; YANG Song; WANG Xun; YE Zi; DONG Hongliang; ZHU Feng; YU Huanhuan; LÜ Yingying; YU Zhongliang

doi:10.1016/S1872-5813(23)60410-4

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2024 > Corrected proof

WANG Bixi, LIU Zeyu, WU Yabei, YANG Yanyan, YANG Song, WANG Xun, YE Zi, DONG Hongliang, ZHU Feng, YU Huanhuan, LÜ Yingying, YU Zhongliang. Multi-site Co2P catalyst derived from soybean biomass for dehydrogenation of formic acid[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(23)60410-4

Citation:

WANG Bixi, LIU Zeyu, WU Yabei, YANG Yanyan, YANG Song, WANG Xun, YE Zi, DONG Hongliang, ZHU Feng, YU Huanhuan, LÜ Yingying, YU Zhongliang. Multi-site Co₂P catalyst derived from soybean biomass for dehydrogenation of formic acid[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(23)60410-4

Citation:

PDF( 5673 KB)

Multi-site Co₂P catalyst derived from soybean biomass for dehydrogenation of formic acid

doi: 10.1016/S1872-5813(23)60410-4

WANG Bixi^{1, 2
,},
LIU Zeyu^2
,,
WU Yabei^1
,,
YANG Yanyan^{1
,
,},
YANG Song^2
,,
WANG Xun^{3, 4},
YE Zi^5
,,
DONG Hongliang^5
,,
ZHU Feng^1
,,
YU Huanhuan^1
,,
LÜ Yingying^1
,,
YU Zhongliang^{1
,
,}

1.
School of Chemistry and Environmental Sciences, Shangrao Normal University, Shangrao 334001, China
2.
College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
3.
College of Safety and Emergency Management Engineering, Taiyuan University of Technology, Taiyuan 030024, China
4.
Shanxi Coking Coal Group Co. LTD, Taiyuan 030024, China
5.
Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, China

Funds: The project was supported by the National Natural Science Foundation of China (22169017, 22366034), Natural Science Foundation of Jiangxi Province (20224BAB203026), the Fundamental Research Program of Shanxi Province (202103021223115), the Science and Technology Project of Jiangxi Education Department (GJJ201709, GJJ2201823, GJJ2201824, GJJ2201830), and the Subsidy Project after R&D Investment of Shangrao City (SKB2021002, 2023AB017, 2023AB014, SKB2021017).

More Information

Author Bio:
School of Chemistry and Environmental Sciences, Shangrao Normal University, Shangrao 334001, China; E-mail:yangyy0927@163.com

School of Chemistry and Environmental Sciences, Shangrao Normal University, Shangrao 334001, China; E-mail:yzh2401@126.com
Corresponding author: E-mail: yangyy0927@163.com; yzh2401@126.com
Received Date: 2023-12-15
Accepted Date: 2024-01-24
Rev Recd Date: 2024-01-21

Available Online: 2024-02-26

Abstract

Abstract

Formic acid (FA) is a sustainable liquid organic hydrogen carrier and the catalyst for hydrogen production from FA has received significant attention. However, the development of efficient non-noble metal catalysts still remains challenges. In this work, we provide a technologically rather simple and environmental-friendly strategy to synthesize Co₂P catalyst for dehydrogenation of FA by pyrolyzing soybean powder and cobalt salt. The K-containing solid bases in catalyst could act as Lewis acid sites for the HCOO⁻ intermediate adsorption while the self-doped N could act as Lewis base sites to enhance the H⁺ adsorption. The P contained in soybean could combine with Co to form Co₂P for H−C bond cleavage of HCOO⁻. At a Co(NO₃)₂·6H₂O/soybean mass ratio of 1∶15, the as prepared Co₂P catalyst demonstrated a gas production rate of 237.47 mL/(g·h) and a good stability. This study provides a novel strategy to develop non-noble metal heterogeneous catalysts for FA dehydrogenation.
- formic acid,
- heterogeneous catalyst,
- biomass,
- dehydrogenation

FullText(HTML)

References(45)

References

[1]	GRASEMANN M, LAURENCZY G. Formic acid as a hydrogen source - recent developments and future trends[J]. Energy Environ Sci,2012,5(8):8171−8181. doi: 10.1039/c2ee21928j
[2]	PRETI D, RESTA C, SQUARCIALUPI S, et al. Carbon dioxide hydrogenation to formic acid by using a heterogeneous gold catalyst[J]. Angew Chemi,2011,123(52):12759−12762. doi: 10.1002/ange.201105481
[3]	CHEN X, LIU Y, WU J. Sustainable production of formic acid from biomass and carbon dioxide[J]. Mol Catal,2020,483:110716. doi: 10.1016/j.mcat.2019.110716
[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]	MARS P, SCHOLTEN J J F, ZWIETERING P. The catalytic decomposition of formic acid[J]. Adv Catal,1963,14:35−113.
[6]	WANG Z L, YAN J M, WANG H L, et al. Q. Pd/C synthesized with citric acid: An efficient catalyst for hydrogen generation from formic acid/sodium formate[J]. Sci Rep,2012,2:1−6.
[7]	ZHANG Z, LUO Y, LIU S, et al. A PdAg-CeO₂ Nanocomposite anchored on mesoporous carbon: A highly efficient catalyst for hydrogen production from formic acid at room temperature[J]. J Mater Chem A: Mater,2019,7(37):21438−21446. doi: 10.1039/C9TA06987A
[8]	LUO Y, YANG Q, NIE W, et al. Anchoring IrPdAu nanoparticles on NH₂-SBA-15 for fast hydrogen production from formic acid at room temperature[J]. ACS Appl Mater Interfaces,2020,12(7):8082−8090. doi: 10.1021/acsami.9b16981
[9]	BULLOCK R M, CHE J G, GAGLIARDI L, et al. Using nature’s blueprint to expand catalysis with earth-abundant metals[J]. Science,2020,369(6505):eabc3183. doi: 10.1126/science.abc3183
[10]	DUAN J, XIANG Z, ZHANG H, et al. Pd-Co₂P nanoparticles supported on N-doped biomass-based carbon microsheet with excellent catalytic performance for hydrogen evolution from formic acid[J]. Appl Surf Sci,2020,530:147191. doi: 10.1016/j.apsusc.2020.147191
[11]	CAO S, CHEN Y, WANG H, et al. Ultrasmall CoP nanoparticles as efficient cocatalysts for photocatalytic formic acid dehydrogenation[J]. Joule,2018,2(3):549−557. doi: 10.1016/j.joule.2018.01.007
[12]	KOÓS á, SOLYMOSI F. Production of CO-free H₂ by formic acid decomposition over Mo₂C/carbon catalysts[J]. Catal Lett,2010,138(1/2):23−27. doi: 10.1007/s10562-010-0375-3
[13]	WANG B, YANG S, YU Z, et al. Performance modulation strategies of heterogeneous catalysts for formic acid dehydrogenation: A review[J]. Mater Today Commun,2022,31:103617. doi: 10.1016/j.mtcomm.2022.103617
[14]	JIA L, BULUSHEV D A, PODYACHEVA O Y, et al. Pt nanoclusters stabilized by N-doped carbon nanofibers for hydrogen production from formic acid[J]. J Catal,2013,307:94−102. doi: 10.1016/j.jcat.2013.07.008
[15]	YU Z, AN X, 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
[16]	YU Z, YANG Y, YANG S, et al. Selective dehydrogenation of aqueous formic acid over multifunctional γ-Mo₂N catalysts at a temperature lower than 100 ℃[J]. Appl Catal B: Environ,2022,313:121445. doi: 10.1016/j.apcatb.2022.121445
[17]	BULUSHEV D A, JIA L, BELOSHAPKIN S, et al. Improved hydrogen production from formic acid on a Pd/C catalyst doped by potassium[J]. Chem Commun (Camb),2012,48(35):4184−4186. doi: 10.1039/c2cc31027a
[18]	JIA L, BULUSHEV D A, BELOSHAPKIN S, et al. Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst[J]. Appl Catal B: Environ,2014,160−161:35−43.
[19]	WANG G, PENG H, QIAO X, et al. Biomass-derived porous heteroatom-doped carbon spheres as a high-performance catalyst for the oxygen reduction reaction[J]. Int J Hydrogen Energy,2016,41(32):14101−14110. doi: 10.1016/j.ijhydene.2016.06.023
[20]	JI T, CHEN L, MU L, et al. Green processing of plant biomass into mesoporous carbon as catalyst support[J]. Chem Eng J,2016,295:301−308. doi: 10.1016/j.cej.2016.03.033
[21]	MATSAGAR B M, YANG R X, DUTTA S, et al. Recent progress in the development of biomass-derived nitrogen-doped porous carbon[J]. J Mater Chem A: Mater,2021,9(7):3703−3728. doi: 10.1039/D0TA09706C
[22]	LIU F, PENG H, QIAO X, et al. High-performance doped carbon electrocatalyst derived from soybean biomass and promoted by zinc chloride[J]. Int J Hydrogen Energy,2014,39(19):10128−10134. doi: 10.1016/j.ijhydene.2014.04.176
[23]	LIU X, ZHOU Y, ZHOU W, et al. Biomass-derived nitrogen self-doped porous carbon as effective metal-free catalysts for oxygen reduction reaction[J]. Nanoscale,2015,7(14):6136−6142. doi: 10.1039/C5NR00013K
[24]	BEDA A, LE MEINS J M, TABERNA P L, et al. Impact of biomass inorganic impurities on hard carbon properties and performance in Na-Ion batteries[J]. Sustainable Mater Technol,2020,26:e00227. doi: 10.1016/j.susmat.2020.e00227
[25]	ZHU Y, XU G, ZHANG X, et al. Hierarchical porous carbon derived from soybean hulls as a cathode matrix for lithium-sulfur batteries[J]. J Alloys Compd,2017,695:2246−2252. doi: 10.1016/j.jallcom.2016.11.075
[26]	PU Z, ZHANG C, AMIINU I S, et al. General strategy for the synthesis of transition-metal phosphide/N-doped carbon frameworks for hydrogen and oxygen evolution[J]. ACS Appl Mater Interfaces,2017,9(19):16187−16193. doi: 10.1021/acsami.7b02069
[27]	XIE H, ZENG D, DU B, et al. Co₂P encapsulated in N, O co-doped carbons as bifunctional electrocatalysts for oxygen evolution and reduction reactions[J]. Int J Hydrogen Energy,2023,48(25):9273−9284. doi: 10.1016/j.ijhydene.2022.11.336
[28]	YANG J, GUO D, ZHAO S, et al. Cobalt phosphides nanocrystals encapsulated by P-doped carbon and married with P-doped graphene for overall water splitting[J]. Small,2019,15(10):1804546. doi: 10.1002/smll.201804546
[29]	XU Y, MO Y, TIAN J, et al. The synergistic effect of graphitic N and pyrrolic N for the enhanced photocatalytic performance of nitrogen-doped graphene/TiO₂ nanocomposites[J]. Appl Catal B: Environ,2016,181:810−817. doi: 10.1016/j.apcatb.2015.08.049
[30]	HU L, HU Y, LIU R, et al. Co-based MOF-derived Co/CoN/Co₂P ternary composite embedded in N- and P-doped carbon as bifunctional nanocatalysts for efficient overall water splitting[J]. Int J Hydrogen Energy,2019,44(23):11402−11410. doi: 10.1016/j.ijhydene.2019.03.157
[31]	JIANG S, WU M, XIAO T, et al. Tailoring the activity of electrocatalytic methanol oxidation on cobalt hydroxide by the incorporation of catalytically inactive zinc ions[J]. ACS Appl Mater Interfaces,2023,15(48):55870−55876. doi: 10.1021/acsami.3c13624
[32]	HUANG T, XU G, DING H, et al. Ultrafine cobalt molybdenum phosphide nanoparticles embedded in crosslinked nitrogen-doped carbon nanofiber as efficient bifunctional catalyst for overall water splitting[J]. J Colloid Interface Sci,2022,625:956−964. doi: 10.1016/j.jcis.2022.06.093
[33]	LONI E, SIADATI M H, SHOKUHFAR A. Mesoporous cobalt-cobalt phosphide electrocatalyst for water splitting[J]. Mater Today Energy,2020,16:100398. doi: 10.1016/j.mtener.2020.100398
[34]	MIYAKOSHI A, UENO A, ICHIKAWA M. XPS and TPD characterization of manganese-substituted iron-potassium oxide catalysts which are selective for dehydrogenation of ethylbenzene into styrene[J]. Appl Catal A: Gen,2001,219(1/2):249−258. doi: 10.1016/S0926-860X(01)00697-4
[35]	ZHAO S, LI C, HUANG H, et al. Phosphate functionalized activated carbon as an efficient metal-free electrocatalyst for the oxygen reduction reaction[J]. New J Chem,2015,39(11):8881−8886. doi: 10.1039/C5NJ01270H
[36]	YANG N, ZHAO Y, ZHANG H, et al. Sintering activated atomic palladium catalysts with high-temperature tolerance of ~1, 000°C[J]. Cell Rep Phys Sci,2021,2(1):100287. doi: 10.1016/j.xcrp.2020.100287
[37]	LIU, Z, YANG S, YANG Y, et al. Efficient hydrogen production from high-concentration aqueous formic acid over bio-based γ-Mo₂N catalysts[J]. Carbon Res Convers, 2023: 100209.
[38]	LIU Q, YANG X, HUANG Y, et al. A schiff base modified gold catalyst for green and efficient H₂ production from formic acid[J]. Energy Environ Sci,2015,8(11):3204−3207. doi: 10.1039/C5EE02506K
[39]	LI M, CHEN S, JIANG Q, et al. Origin of the activity of Co-N-C catalysts for chemoselective hydrogenation of nitroarenes[J]. ACS Catal,2021,11(5):3026−3039. doi: 10.1021/acscatal.0c05479
[40]	XU D, ZHAO H, DONG Z, et al. Catalytically active Co-N_x species stabilized on nitrogen-doped porous carbon for efficient hydrogenation and dehydrogenation of N-heteroarenes[J]. ChemCatChem,2020,12(17):4406−4415. doi: 10.1002/cctc.202000826
[41]	TANG C, SURKUS A E, CHEN F, et al. A stable nanocobalt catalyst with highly dispersed CoNx active sites for the selective dehydrogenation of formic acid[J]. Angew Chem Int Ed Eng,2017,56(52):16616−16620.
[42]	LIU M, XU Y, MENG Y, et al. Heterogeneous catalysis for carbon dioxide mediated hydrogen storage technology based on formic acid[J]. Adv Energy Mater,2022,12(31):2200817.
[43]	JIA L, BULUSHEV D A, ROSS J R H. Formic acid decomposition over palladium based catalysts doped by potassium carbonate[J]. Catal Today,2016,259:453−459. doi: 10.1016/j.cattod.2015.04.008
[44]	BULUSHEV D A, ZACHARSKA M, GUO, Y, et al. CO-Free hydrogen production from decomposition of formic acid over Au/Al₂O₃ catalysts doped with potassium ions[J]. Catal Commun,2017,92:86−89. doi: 10.1016/j.catcom.2017.01.011
[45]	ZHAO H B, XU W T, SONG Q, et al. Effect of steam and SiO₂ on the release and transformation of K₂CO₃ and KCl during biomass thermal conversion[J]. Energy Fuels,2018,32(9):9633−9639. doi: 10.1021/acs.energyfuels.8b02269