Enhanced formic acid production for CO₂ photocatalytic reduction over Pd/H-TiO₂ catalyst

Abstract

The photocatalytic reduction of CO₂ into formic acid is a feasible approach to alleviate the effects of global climate change and achieve chemical energy storage. It is important to design highly active photocatalysts to improve the selectivity and yield of formic acid. In this study, TiO₂-based catalysts were prepared and loaded with Pd nanoparticles via an impregnation process. The Pd/H-TiO₂ catalyst demonstrated superior CO₂ reduction activity and a high formic acid production rate of 14.14 mmol_cat·g^–1·h^–1. The excellent catalytic performance observed in the presence of a Pd/H-TiO₂ catalyst is ascribed to the synergy between O_v and Pd. The presence of O_v led to increase in CO₂ adsorption while Pd loading enhanced the photogenerated electron-hole pair separation. Electron transfer from H-TiO₂ to Pd also contributed to CO₂ activation.

Keywords

CO₂ reduction / formic acid / photocatalysis / TiO₂ catalyst

参考文献

[1] Yuan Z M , Zhu X L , Gao X Q , An C H , Wang Z , Zuo C , Dionysiou D D , He H , Jiang Z Y . Enhancing photocatalytic CO₂ reduction with TiO₂-based materials: strategies, mechanisms, challenges, and perspectives. Environmental Science and Ecotechnology, 2024, 20: 100368

[2] Wang S W , Wang L G , Wang D S , Li Y D . Recent advances of single-atom catalysts in CO₂ conversion. Energy & Environmental Science, 2023, 16(7): 2759–2803

[3] Pan F P , Li B Y , Deng W , Du Z C , Gang Y , Wang G F , Li Y . Promoting electrocatalytic CO₂ reduction on nitrogen-doped carbon with sulfur addition. Applied Catalysis B: Environmental, 2019, 252: 240–249

[4] Liu M X , Xu Y K , Meng Y , Wang L J , Wang H , Huang Y C , Onishi N , Wang L , Fan Z J , Himeda Y . Heterogeneous catalysis for carbon dioxide mediated hydrogen storage technology based on formic acid. Advanced Energy Materials, 2022, 12(31): 2200817

[5] Lv C C , Bai X H , Ning S B , Song C X , Guan Q Q , Liu B , Li Y G , Ye J H . Nanostructured materials for photothermal carbon dioxide hydrogenation: regulating solar utilization and catalytic performance. ACS Nano, 2023, 17(3): 1725–1738

[6] Zhang S Q , Yu H Y , Wang Y , Yan Y X , Dai J , Shu D J , Wu X L . Surface dual metal occupations in Fe-doped Fe_xBi_2–xO₃ induce highly efficient photocatalytic CO₂ reduction. ACS Applied Materials & Interfaces, 2023, 15(20): 25049–25057

[7] Saito D , Tamaki Y , Ishitani O . Photocatalysis of CO₂ reduction by a Ru(II)-Ru(II) supramolecular catalyst adsorbed on Al₂O₃. ACS Catalysis, 2023, 13(7): 4376–4383

[8] Pan H Q , Heagy M D . Photons to formate: a review on photocatalytic reduction of CO₂ to formic acid. Nanomaterials, 2020, 10(12): 2422

[9] Xiong J , Yang A J , Sun Q , Gao H X , Zhang H Y , Mao Y , Liang Z W . Insights into CO₂ activation and charge transfer in photocatalytic reduction of CO₂ on pure and metal single atom modified TiO₂ surfaces. Molecular Catalysis, 2023, 547: 113370

[10] Khan H , Shah M U H . Modification strategies of TiO₂ based photocatalysts for enhanced visible light activity and energy storage ability: a review. Journal of Environmental Chemical Engineering, 2023, 11(6): 111532

[11] Li G H , Sun Y Y , Zhang Q M , Gao Z , Sun W , Zhou X X . Ag quantum dots modified hierarchically porous and defective TiO₂ nanoparticles for improved photocatalytic CO₂ reduction. Chemical Engineering Journal, 2021, 410: 128397

[12] Wu Y W , Yan L , Yu Y Q , Jing C Y . Photocatalytic CO₂ reduction to CH₄ on iron porphyrin supported on atomically thin defective titanium dioxide. Catalysis Science & Technology, 2021, 11(18): 6103–6111

[13] Ali Khan A , Tahir M . Synergistic effect of Co/La in oxygen vacancy rich ternary CoAlLa layered double hydroxide with enhanced reductive sites for selective photoreduction of CO₂ to CH₄. Energy & Fuels, 2021, 35(10): 8922–8943

[14] Zhao H L , Pan F P , Li Y . A review on the effects of TiO₂ surface point defects on CO₂ photoreduction with H₂O. Journal of Materiomics, 2017, 3(1): 17–32

[15] Song G X , Lang X F , Huo C X , Ren S H , Wang Y J , Tang Z K , Chen X G . Mechanism of photocatalytic reduction of CO₂ to CH₄ on F-doped defective anatase TiO₂ (101) surface: a density functional theory study. Surface Science, 2023, 730: 122247

[16] Wang S , Nie X W , Lin J B , Ding F S , Song C S , Guo X W . Computational design of single-atom modified Ti-MOFs for photocatalytic CO₂ reduction to C1 chemicals. ChemSusChem, 2024, 17(8): e202301619

[17] Wei F , Luo T , Wang Y , Kong L C , Feng J J , Li Z Q , Lu J Q , Yang F . Boosting CO₂ electroreduction to formate via in-situ formation of ultrathin Bi nanosheets decorated with monodispersed Pd nanoparticles. Journal of Catalysis, 2023, 424: 50–63

[18] Zhang F , Li Y H , Qi M Y , Tang Z R , Xu Y J . Boosting the activity and stability of Ag-Cu₂O/ZnO nanorods for photocatalytic CO₂ reduction. Applied Catalysis B: Environmental, 2020, 268: 118380

[19] Shi Y X , Li L L , Xu Z , Guo F , Li Y , Shi W L . Synergistic coupling of piezoelectric and plasmonic effects regulates the Schottky barrier in Ag nanoparticles/ultrathin g-C₃N₄ nanosheets heterostructure to enhance the photocatalytic activity. Applied Surface Science, 2023, 616: 156466

[20] Jin B B , Ye X , Zhong H , Jin F M . Light-driven hydrogenation of bicarbonate into formate over nano-Pd/TiO₂. ACS Sustainable Chemistry & Engineering, 2020, 8(17): 6798–6805

[21] Zheng M Y , Yang J , Fan W L , Zhao X . Oxygen vacancy and nitrogen doping collaboratively boost performance and stability of TiO₂-supported Pd catalysts for CO₂ photoreduction: a DFT study. Physical Chemistry Chemical Physics, 2021, 23(43): 24801–24813

[22] Li J , Zhou H , Zhuo H , Wei Z Z , Zhuang G L , Zhong X , Deng S W , Li X N , Wang J G . Oxygen vacancies on TiO₂ promoted the activity and stability of supported Pd nanoparticles for the oxygen reduction reaction. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(5): 2264–2272

[23] Vequizo J J M , Kato K , Amano F , Yamakata A . Unfolding the impact of H₂-reduction treatment in enhancing the photocatalytic activity of rutile TiO₂ based on photocarriers dynamics. Journal of Physical Chemistry C, 2023, 127(22): 10411–10418

[24] Sang L X , Zhao Y X , Burda C . TiO₂ nanoparticles as functional building blocks. Chemical Reviews, 2014, 114(19): 9283–9318

[25] Zhong J B , Lu Y , Jiang W D , Meng Q M , He X Y , Li J Z , Chen Y Q . Characterization and photocatalytic property of Pd/TiO₂ with the oxidation of gaseous benzene. Journal of Hazardous Materials, 2009, 168(2-3): 1632–1635

[26] Yilmaz P , Lacerda A M , Larrosa I , Dunn S . Photoelectrocatalysis of rhodamine B and solar hydrogen production by TiO₂ and Pd/TiO₂ catalyst systems. Electrochimica Acta, 2017, 231: 641–649

[27] Phan T N , Park Y K , Lee I G , Ko C H . Enhancement of C–O bond cleavage to afford aromatics in the hydrodeoxygenation of anisole over ruthenium-supporting mesoporous metal oxides. Applied Catalysis A, General, 2017, 544: 84–93

[28] Samsudin E M , Hamid S B A , Juan J C , Basirun W J , Kandjani A E . Surface modification of mixed-phase hydrogenated TiO₂ and corresponding photocatalytic response. Applied Surface Science, 2015, 359: 883–896

[29] Liu L , Yu P Y , Chen X B , Mao S S , Shen D Z . Hydrogenation and disorder in engineered black TiO₂. Physical Review Letters, 2013, 111(6): 065505

[30] Mo L B , Wang Y , Bai Y , Xiang Q Y , Li Q , Yao W Q , Wang J O , Ibrahim K , Wang H H , Wan C H . . Hydrogen impurity defects in rutile TiO₂. Scientific Reports, 2015, 5(1): 17634

[31] Zhang Y S , Liu J X , Qian K , Jia A P , Li D , Shi L , Hu J , Zhu J F , Huang W X . Structure sensitivity of Au-TiO₂ strong metal-support interactions. Angewandte Chemie International Edition, 2021, 60(21): 12074–12081

[32] Li J L , Zhang M , Guan Z J , Li Q Y , He C Q , Yang J J . Synergistic effect of surface and bulk single-electron-trapped oxygen vacancy of TiO₂ in the photocatalytic reduction of CO₂. Applied Catalysis B: Environmental, 2017, 206: 300–307

[33] Jiang D L , Zhou Y M , Zhang Q X , Song Q , Zhou C J , Shi X L , Li D . Synergistic integration of AuCu Co-catalyst with oxygen vacancies on TiO₂ for efficient photocatalytic conversion of CO₂ to CH₄. ACS Applied Materials & Interfaces, 2021, 13(39): 46772–46782

[34] Zhu Q H , Deng Z S , Xie H J , Xing M Y , Zhang J L . Investigation of concerted proton-electron donors for promoting the selective production of HCOOH in CO₂ photoreduction. ACS Catalysis, 2023, 13(5): 3254–3262

[35] Peña R , Romero R , Amado-Piña D , Natividad R . Cu/TiO₂ photo-catalyzed CO₂ chemical reduction in a multiphase capillary reactor. Topics in Catalysis, 2024, 67(5-8): 377–393

[36] Zhang H N , Li Y F , Wang J Z , Wu N N , Sheng H , Chen C C , Zhao J C . An unprecedent hydride transfer pathway for selective photocatalytic reduction of CO₂ to formic acid on TiO₂. Applied Catalysis B: Environmental, 2021, 284: 119692

[37] Iguchi S , Kikkawa S , Teramura K , Hosokawa S , Tanaka T . Investigation of the electrochemical and photoelectrochemical properties of Ni-Al LDH photocatalysts. Physical Chemistry Chemical Physics, 2016, 18(20): 13811–13819

[38] Huang X Y , Lei R , Yuan J , Gao F , Jiang C K , Feng W H , Zhuang J D , Liu P . Insight into the piezo-photo coupling effect of PbTiO₃/CdS composites for piezo-photocatalytic hydrogen production. Applied Catalysis B: Environmental, 2021, 282: 119586

[39] Zheng D , Xue Y F , Wang J , Varbanov P S , Klemes J J , Yin C . Nanocatalysts in photocatalytic water splitting for green hydrogen generation: challenges and opportunities. Journal of Cleaner Production, 2023, 414: 137700

[40] Quan Q , Xie S J , Weng B , Wang Y , Xu Y J . Revealing the double-edged sword role of graphene on boosted charge transfer versus active site control in TiO₂ nanotube arrays@RGO/MoS₂ heterostructure. Small, 2018, 14(21): 1704531

[41] Basumatary R , Basumatary B , Konwar D , Ramchiary A . Tailored highly efficient Co-doped TiO₂/CoTiO₃ heterojunction photocatalyst for methylene blue degradation under visible light. Journal of the Korean Ceramic Society, 2023, 60(3): 547–559

[42] Ren J , Ouyang S , Xu H , Meng X , Wang T , Wang D , Ye J . Targeting activation of CO₂ and H₂ over Ru-loaded ultrathin layered double hydroxides to achieve efficient photothermal CO₂ methanation in flow-type system. Advanced Energy Materials, 2017, 7(5): 1601657

[43] Chang L , Besteiro L V , Sun J C , Santiago E Y , Gray S K , Wang Z M , Govorov A O . Electronic structure of the plasmons in metal nanocrystals: fundamental limitations for the energy efficiency of hot electron generation. ACS Energy Letters, 2019, 4(10): 2552–2568

[44] Cao Y H , Zhang R Y , Zhou T L , Jin S M , Huang J D , Ye L Q , Huang Z A , Wang F , Zhou Y . Zhou Y. B–O bonds in ultrathin boron nitride nanosheets to promote photocatalytic carbon dioxide conversion. ACS Applied Materials & Interfaces, 2020, 12(8): 9935–9943

[45] Zindrou A , Deligiannakis Y . Quantitative in situ monitoring of Cu-atom release by Cu₂O nanocatalysts under photocatalytic CO₂ reduction conditions: new insights into the photocorrosion mechanism. Nanomaterials (Basel, Switzerland), 2023, 13(11): 1773

[46] Li A , Cao Q , Zhou G Y , Schmidt B , Zhu W J , Yuan X T , Huo H L , Gong J L , Antonietti M . Three-phase photocatalysis for the enhanced selectivity and activity of CO₂ reduction on a hydrophobic surface. Angewandte Chemie International Edition, 2019, 58(41): 14549–14555

[47] Qu T X , Wei S Z , Xiong Z , Zhang J Y , Zhao Y C . Progress and prospect of CO₂ photocatalytic reduction to methanol. Fuel Processing Technology, 2023, 251: 107933

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (Grant No. 2022YFE0208400), the Natural Science Foundation of Shanxi Province (Grant No. 202303021221019), the Fundamental Research Funds for the Central Universities (Grant No. 2022ZFJH004), and the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (Grant No. 2021SX-FR002).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2485-2 and is accessible for authorized users.

版权

2024 Higher Education Press