Au/Co3O4-ZnO催化剂上CO2-丙三醇羰基化合成丙三醇碳酸酯

doi:10.3866/PKU.WHXB202308005

Abstract

Abstract:

Glycerol carbonylation with CO₂ to synthesize glycerol carbonate is a promising approach for CO₂ utilization. This reaction can be achieved through a thermally-driven catalytic pathway, but it is constrained by thermodynamic equilibrium. In the present study, we introduced solar energy into the reaction system to enable a photo-thermal synergistic catalytic reaction, breaking through the thermodynamic limitations. We developed a series of xAu/20Co₃O₄-ZnO catalysts, where Co₃O₄-ZnO, a composite of p-type semi-conductor Co₃O₄ and n-type semi-conductor ZnO, exhibited a heterojunction structure, and Au nanoparticles loaded onto the surface of Co₃O₄-ZnO revealed the localized surface plasmon resonance (LSPR). We investigated the ability of xAu/Co₃O₄-ZnO to absorb visible light absorption, the efficiency of separating photo-generated hole-electron pairs, and the impact of Au on the photothermal synergistic catalytic performances of Au/Co₃O₄-ZnO catalysts. We also examined the effects of Au doping on the bulk and surface properties, including crystalline structures, morphologies, specific surface areas and pore structures, the binding energies of the elements, surface acid-base sites, and reduction behaviors of xAu/Co₃O₄-ZnO. Our findings revealed that the heterojunction structure of Au/20Co₃O₄-ZnO facilitated visible light absorption and hole-electron pair separation. The size of Au nano-particles (NPs) loaded on Co₃O₄-ZnO surface was approximately 50 nm. The loading of Au altered the electron density of Co and Zn, improved the reducibility of Co species, and enhanced the presence of oxygen vacancies on Co₃O₄-ZnO surface. The LSPR of Au NPs further enhanced the visible light absorption capacity of Au/20Co₃O₄-ZnO, and improved the separating of photogenerated hole-electron pairs, thus enhancing the photothermal catalytic performances. With the optimizing conditions (150 ℃, 5 MPa, 6 h, and 225 W visible light irradiation), the 2%Au/20Co₃O₄-ZnO catalyst demonstrated excellent performances, yielding a glycerol carbonate yield of 6.5%. This study is expected to serve as a reference for the rational design of improved photothermal catalysts for glycerol carbonylation with CO₂ to produce glycerol carbonate in the future.

Key words: CO₂ utilization, Glycerol carbonylation, Glycerol carbonate, Plasmonic metal, Photo-thermal catalysis

Yajin Li, Huimin Liu, Lan Ma, Jiaxiong Liu, Dehua He. Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO₂ over Au/Co₃O₄-ZnO Catalyst[J]. Acta Phys. -Chim. Sin. 2024, 40(9), 2308005. doi: 10.3866/PKU.WHXB202308005

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References 54

1	Hepburn C.; Adlen E.; Beddington J.; Carter E. A.; Fuss S.; Mac Dowell N.; Minx J. C.; Smith P.; Williams C. K. Nature 2019, 575(7781), 87. doi: 10.1038/s41586-019-1681-6
2	Jiang X.; Nie X. W.; Guo X. W.; Song C. S.; Chen J. G. G. Chem. Rev. 2020, 120(15), 7984. doi: 10.1021/acs.chemrev.9b00723
3	Huo Y.; Zhang J. F.; Dai K.; Li Q.; Lv J. L.; Zhu G. P.; Liang C. H. Appl. Catal. B-Environ. 2019, 241, 528. doi: 10.1016/j.apcatb.2018.09.073
4	Chen Y. L.; Wang Z.; Zhong Z. Q. Renew. Energy 2019, 131, 208. doi: 10.1016/j.renene.2018.07.047
5	Bekun F. V.; Alola A. A.; Sarkodie S. A. Sci. Total Environ. 2019, 657, 1023. doi: 10.1016/j.scitotenv.2018.12.104
6	Kibria M. G.; Edwards J. P.; Gabardo C. M.; Dinh C. T.; Seifitokaldani A.; Sinton D.; Sargent E. H. Adv. Mater. 2019, 31, 1807166. doi: 10.1002/adma.201807166
7	Zhao Y. F.; Waterhouse G. I. N.; Chen G. B.; Xiong X. Y.; Wu L. Z.; Tung C. H.; Zhang T. R. Chem. Soc. Rev. 2019, 48(7), 1972. doi: 10.1039/c8cs00607e
8	Aitbekova A.; Wu L. H.; Wrasman C. J.; Boubnov A.; Hoffman A. S.; Goodman E. D.; Bare S. R.; Cargnello M. J. Am. Chem. Soc. 2018, 140(42), 13736. doi: 10.1021/jacs.8b07615
9	Frei M. S.; Capdevila-Cortada M.; Garcia-Muelas R.; Mondelli C.; Lopez N.; Stewart J. A.; Ferre D. C.; Perez-Ramirez J. J. Catal. 2018, 361, 313. doi: 10.1016/j.jcat.2018.03.014
10	Ma Z. Q.; Porosoff M. D. ACS Catal. 2019, 9(3), 2639. doi: 10.1021/acscatal.8b05060
11	Nie X. W.; Jiang X.; Wang H. Z.; Luo W. J.; Janik M. J.; Chen Y. G.; Guo X. W.; Song C. S. ACS Catal. 2018, 8(6), 4873. doi: 10.1021/acscatal.7b04150
12	Yang W. W.; Liu H. M.; Li Y. M.; Zhang J.; Wu H.; He D. H. Catal. Today 2016, 259, 438. doi: 10.1016/j.cattod.2015.04.012
13	Liu H. M.; Li Y. J.; He D. H. Energy Technol. 2020, 8(8), 1900493. doi: 10.1002/ente.201900493
14	Chang T.; Tamura M.; Nakagawa Y.; Fukaya N.; Choi J. C.; Mishima T.; Matsumoto S.; Hamura S.; Tomishige K. Green Chem. 2020, 22(21), 7321. doi: 10.1039/d0gc02717k
15	Truong C. C.; Mishra D. K. J. CO₂ Util. 2020, 41, 101252. doi: 10.1016/j.jcou.2020.101252
16	Liu J. X.; Li Y. M.; Zhang J.; He D. H. Appl. Catal. A-Gen. 2016, 513, 9. doi: 10.1016/j.apcata.2015.12.030
17	Li H. G.; Jiao X.; Li L.; Zhao N.; Xiao F. K.; Wei W.; Sun Y. H.; Zhang B. S. Catal. Sci. Technol. 2015, 5(2), 989. doi: 10.1039/c4cy01237b
18	Su X. L. N.; Lin W. W.; Cheng H. Y.; Zhang C.; Wang Y.; Yu X. J.; Wu Z. J.; Zhao F. Y. Green Chem. 2017, 19(7), 1775. doi: 10.1039/c7gc00260b
19	Zhang J.; He D. H. J. Colloid Interface Sci. 2014, 419, 31. doi: 10.1016/j.jcis.2013.12.049
20	Huang X. Q.; Tang S. H.; Mu X. L.; Dai Y.; Chen G. X.; Zhou Z. Y.; Ruan F. X.; Yang Z. L.; Zheng N. F. Nat. Nanotechnol. 2011, 6(1), 28. doi: 10.1038/nnano.2010.235
21	Wang J.; Li Y. Y.; Deng L.; Wei N. N.; Weng Y. K.; Dong S.; Qi D. P.; Qiu J.; Chen X. D.; Wu T. Adv. Mater. 2017, 29(3), 1603730. doi: 10.1002/adma.201603730
22	Reithofer M. R.; Sum Y. N.; Zhang Y. G. Green Chem. 2013, 15(8), 2086. doi: 10.1039/c3gc40790j
23	Park C. Y.; Huy N. P.; Shin E. W. Mol. Catal. 2017, 435, 99. doi: 10.1016/j.mcat.2017.03.025
24	Li Y. J.; Liu H. M.; Ma L.; Liu J. X.; He D. H. Catal. Sci. Technol. 2021, 11(3), 1007. doi: 10.1039/d0cy01821j
25	Liu H. M.; Li Y. J.; Ma L.; Liu J. X.; He D. H. Fuel 2022, 315, 123294. doi: 10.1016/j.fuel.2022.123294
26	Gelle A.; Jin T.; de la Garza L.; Price G. D.; Besteiro L. V.; Moores A. Chem. Rev. 2020, 120(2), 986. doi: 10.1021/acs.chemrev.9b00187
27	Xu Y.; Bai P.; Zhou X. D.; Akimov Y.; Png C. E.; Ang L. K.; Knoll W.; Wu L. Adv. Opt. Mater. 2019, 7(9), 1801433. doi: 10.1002/adom.201801433
28	Kim M.; Lee J. H.; Nam J. M. Adv. Sci. 2019, 6(17), 1900471. doi: 10.1002/advs.201900471
29	Madhumitha G.; Fowsiya J.; Gupta N.; Kumar A.; Singh M. J. Phys. Chem. Solids 2019, 127, 43. doi: 10.1016/j.jpcs.2018.12.005
30	Reddy K.; Reddy A. J.; Krishna R. H.; Nagabhushana B. M.; Gopal R. J. Asian Ceram. Soc. 2017, 5(3), 350. doi: 10.1016/j.jascer.2017.06.008
31	Karimi-Maleh H.; Yola M. L.; Atar N.; Orooji Y.; Karimi F.; Kumar P. S.; Rouhi J.; Baghayeri M. J. Colloid Interface Sci. 2021, 592, 174. doi: 10.1016/j.jcis.2021.02.066
32	Lukashuk L.; Yigit N.; Rameshan R.; Kolar E.; Teschner D.; Havecker M.; Knop-Gericke A.; Schlogl R.; Fottinger K.; Rupprechter G. ACS Catal. 2018, 8(9), 8630. doi: 10.1021/acscatal.8b01237
33	Aparna T. K.; Sivasubramanian R.; Dar M. A. J. Alloy. Compd. 2018, 741, 1130. doi: 10.1016/j.jallcom.2018.01.205
34	Yang Y. T.; Jiang K. D.; Guo J.; Li J.; Peng X. L.; Hong B.; Wang X. Q.; Ge H. L. Chem. Eng. J. 2020, 381, 122596. doi: 10.1016/j.cej.2019.122596
35	Wang C.; Lin G.; Zhao J. L.; Wang S. X.; Zhang L. B.; Xi Y. H.; Li X. T.; Ying Y. Chem. Eng. J. 2020, 380, 122511. doi: 10.1016/j.cej.2019.122511
36	Wang J. P.; Wang Z. Y.; Huang B. B.; Ma Y. D.; Liu Y. Y.; Qin X. Y.; Zhang X. Y.; Dai Y. ACS Appl. Mater. Interfaces 2012, 4(8), 4024. doi: 10.1021/am300835p
37	Zheng Y. H.; Chen C. Q.; Zhan Y. Y.; Lin X. Y.; Zheng Q.; Wei K. M.; Zhu J. F. J. Phys. Chem. C 2008, 112(29), 10773. doi: 10.1021/jp8027275
38	Lin X. T.; Li S. J.; He H.; Wu Z.; Wu J. L.; Chen L. M.; Ye D. Q.; Fu M. L. Appl. Catal. B-Environ. 2018, 223, 91. doi: 10.1016/j.apcatb.2017.06.071
39	Chen L. W.; Ding D. H.; Liu C.; Cai H.; Qu Y.; Yang S. J.; Gao Y.; Cai T. M. Chem. Eng. J. 2018, 334, 273. doi: 10.1016/j.cej.2017.10.040
40	Gomes J. R. B.; Ramalho J. P. P.; Illas F. Surf. Sci. 2010, 604(3–4), 428. doi: 10.1016/j.susc.2009.12.009
41	Liu H. M.; Meng X. G.; Dao T. D.; Zhang H. B.; Li P.; Chang K.; Wang T.; Li M.; Nagao T.; Ye J. H. Angew. Chem. Int. Ed. 2015, 54(39), 11545. doi: 10.1002/anie.201504933
42	Liu H. M.; Li M.; Dao T. D.; Liu Y. Y.; Zhou W.; Liu L. Q.; Meng X. G.; Nagao T.; Ye J. H. Nano Energy 2016, 26, 398. doi: 10.1016/j.nanoen.2016.05.045
43	Ashokkumar M.; Muthukumaran S. J. Magn. Magn. Mater. 2015, 374, 61. doi: 10.1016/j.jmmm.2014.08.023
44	Kulal N.; Vetrivel R.; Krishna N. S. G.; Shanbhag G. V. ACS Appl. Nano Mater. 2021, 4(5), 4388. doi: 10.1021/acsanm.0c03166
45	Hu C. C.; Chang C. W.; Yoshida M.; Wang K. H. J. Mater. Chem. A 2021, 9(11), 7048. doi: 10.1039/d0ta12413c
46	Zhang J.; He D. H. J. Chem. Technol. Biotechnol. 2015, 90(6), 1077. doi: 10.1002/jctb.4414
47	Li H. G.; Xin C. L.; Jiao X.; Zhao N.; Xiao F. K.; Li L.; Wei W.; Sun Y. H. J. Mol. Catal. A-Chem. 2015, 402, 71. doi: 10.1016/j.molcata.2015.03.012
48	Liu J. X.; Li Y. J.; Liu H. M.; He D. H. Appl. Catal. B-Environ. 2019, 244, 836. doi: 10.1016/j.apcatb.2018.12.018
49	Ingram D. B.; Christopher P.; Bauer J. L.; Linic S. ACS Catal. 2011, 1(10), 1441. doi: 10.1021/cs200320h
50	Aguado E. R.; Cecilia J. A.; Infantes-Molina A.; Talon A.; Storaro L.; Moretti E.; Rodriguez-Castellon E. Dalton Trans. 2020, 49(13), 3946. doi: 10.1039/c9dt04243a
51	Du H.; Williams C. T.; Ebner A. D.; Ritter J. A. Chem. Mater. 2010, 22(11), 3519. doi: 10.1021/cm100703e
52	Stevens R. W.; Siriwardane R. V.; Logan J. Energy Fuels 2008, 22(5), 3070. doi: 10.1021/ef800209a
53	Reinoso D. M.; Damiani D. E.; Tonetto G. M. Appl. Catal. B- Environ. 2014, 144, 308. doi: 10.1016/j.apcatb.2013.07.026
54	Rakibuddin M.; Ananthakrishnan R. RSC Adv. 2015, 5(83), 68117. doi: 10.1039/c5ra07799k

Catalyst	Lattice oxygen (O_L) ^a	Adsorbed oxygen (O_S) ^b	Hydroxyl group (O_H) ^c
20Co₃O₄-ZnO	10.8%	30.3%	58.9%
0.1%Au/20Co₃O₄-ZnO	11.7%	36.4%	51.9%
0.5%Au/20Co₃O₄-ZnO	13.4%	41.3%	45.3%
2%Au/20Co₃O₄-ZnO	16.3%	52.3%	31.4%

Catalyst	Base sites (μmolCO₂∙g⁻¹)			Total base sites (μmol CO₂∙g⁻¹)
Catalyst	Weak (< 250 ºC)	Medium (250–450 ºC)	Strong (> 450 ºC)	Total base sites (μmol CO₂∙g⁻¹)
20Co₃O₄-ZnO	33.08 (74% ^a)	10.49 (23%)	1.27 (3%)	44.84
0.5%Au/20Co₃O₄-ZnO	22.68 (55%)	3.94 (10%)	14.25 (35%)	40.87
1%Au/20Co₃O₄-ZnO	18.12 (54%)	2.28 (7%)	12.86 (39%)	33.26
2%Au/20Co₃O₄-ZnO	17.86 (53%)	2.06 (6%)	13.40 (40%)	33.32

Support/catalyst	Specific surface area/(m²∙g⁻¹)
20Co₃O₄-ZnO	20.2
0.1%Au/20Co₃O₄-ZnO	19.9
1.0%Au/20Co₃O₄-ZnO	20.9

Recycle number	Glycerol carbonate yield (%)
1	6.5
2	6.3
3	6.2

Catalyst	Reaction conditions	Performance	Reference
Au/Co₃O₄-ZnO	100 mL stainless steel autoclave, 10 mmol glycerol, 0.50 g catalyst, 20 mL dimethyl fumarate, 150 ℃, 5 MPa CO₂, 6 h and 225 W visible light irradiation.	6.5% glycerol carbonate yield.	This work
Zn-doped CeO₂	50 mL high-pressure reactor, 0.92 g glycerol (10 mmol), 0.17 g catalyst, 3.12 g 2-cyanopyridine, 10 mL dimethylformamide, 150 ℃, 40 bar (1 bar = 0.1 MPa) CO₂ pressure, and 5 h.	19.1% glycerol conversion and 18.9% glycerol carbonate yield.	44
La/ZIF-8	100 mL stainless steel autoclave, 0.1 g catalyst, 7 bar CO₂, 150 ℃, in the presence of MgCO₃ as the dehydrating agent.	46.5% glycerol conversion and 35.3% glycerol carbonate yield.	45
CeO₂	100 mL stainless steel autoclave, 10 mmol glycerol, 0.34 g CeO₂, 30 mmol 2-cyanopyridine, 10 mL dimethyl formamide, 150 ℃, 4 MPa and reaction time 5 h.	20.8% glycerol carbonate yield.	16
Cu/La₂O₃	100 mL stainless steel autoclave, glycerol 50 mmol, acetonitrile 10 mL, catalyst 0.08 g, 150 ℃, CO₂ 7 MPa, 3 h.	8.9% glycerol conversion and 29.3% selectivity towards glycerol carbonate.	46
Zn/Al/La/X (X = F, Cl, Br)	50 mL stainless-steel autoclave, 4.60 g glycerol, 0.14 g catalyst and 5.0 mL acetonitrile, CO₂ 4.0 MPa, 170 ℃ for 12 h.	35.5% glycerol conversion and 16.0% glycerol carbonate yield.	47
La₂O₂CO₃-ZnO	100 mL stainless steel autoclave, 0.92 g glycerol, 0.50 g catalyst, 20 mL of N, N-dimethylformamide, 150 ℃, 5.5 MPa CO₂, and reaction time of 6 h, visible light irradiation.	6.9% glycerol conversion and 6.1% glycerol carbonate yield.	24
Au/ZnWO₄-ZnO	100 mL stainless steel autoclave, 10 mmol glycerol, 1.0 g catalyst, 20 mL N, N-dimethylformamide, 5.0 MPa CO₂, 150 ℃, 6 h, with 250 W visible light irradiation.	8.4% glycerol carbonate yield.	48

Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO₂ over Au/Co₃O₄-ZnO Catalyst

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Catalyst	Reaction condition	Glycerol carbonate yield (%)
2%Au/20Co₃O₄-ZnO	Thermal	4.5
2%Au/20Co₃O₄-ZnO	Photo-thermal	6.5
20Co₃O₄-ZnO	Thermal	3.1
20Co₃O₄-ZnO	Photo-thermal	5.3
2%Au/Co₃O₄	Thermal	2.6
2%Au/Co₃O₄	Photo-thermal	3.2
2%Au/ZnO	Thermal	1.3
2%Au/ZnO	Photo-thermal	1.8

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Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO2 over Au/Co3O4-ZnO Catalyst

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Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO₂ over Au/Co₃O₄-ZnO Catalyst