Active Pd nanoclusters supported on nitrogen/amino co-functionalized carbon for highly efficient dehydrogenation of formic acid

Abstract

Supported noble metal catalysts have exhibited satisfactory catalytic performance in the dehydrogenation of liquid chemical hydrogen carriers, in which the supports play a paramount role in conditioning the nature of the active center and thus improving the overall reactivity. Herein, the specially designed nitrogen/amino co-functionalized carbon (NH₂-NC) supports are prepared to load active Pd nanoclusters for efficient dehydrogenation of formic acid (FA). The nitrogen/amino co-functionalization of carbon not only facilitates the Pd nanoclusters evenly dispersed with a mean size of 1.4 nm, but also provides a beneficial metal-support interaction to promote FA dehydrogenation. The as-prepared Pd@NH₂-NC discloses a 100% conversion of FA into CO₂ and H₂ with a remarkable initial turnover frequency (TOF_initial) of 4,892 h^-1 and a low activation energy (E_a) of 28.5 kJ mol^-1 without additive at 298 K. The work proposes a co-functionalization strategy to reasonably design supports for heterogeneous catalysts and may be extended to develop other multi-functionalized supports with different compositions and nanostructures.

Keywords

Formic acid / catalysis / hydrogen production / Pd nanocluster / carbon functionalization

References

[1] Sun Q,Xu Q.Nanopore-supported metal nanocatalysts for efficient hydrogen generation from liquid-phase chemical hydrogen storage materials.Adv Mater2020;32:e2001818

[2] Mboyi CD,Roger J,Kahn ML.The hydrogen-storage challenge: nanoparticles for metal-catalyzed ammonia borane dehydrogenation.Small2021;17:e2102759

[3] Zhong H,Chatterjee M,Xu Q.Formic acid-based liquid organic hydrogen carrier system with heterogeneous catalysts.Adv Sustainable Syst2018;2:1700161

[4] Xu R,Toan S.Thermocatalytic formic acid dehydrogenation: recent advances and emerging trends.J Mater Chem A2021;9:24241-60

[5] Qin X,Xie S.Mechanistic analysis-guided Pd-based catalysts for efficient hydrogen production from formic acid dehydrogenation.ACS Catal2020;10:3921-32

[6] Li X,Rabeah J.Cobalt single-atom catalysts with high stability for selective dehydrogenation of formic acid.Angew Chem Int Ed Engl2020;59:15849-54 PMCID:PMC7540455

[7] Cui Y,Zou Y.Ultrasmall AuPd nanoclusters on amine-functionalized carbon blacks as high-performance bi-functional catalysts for ethanol electrooxidation and formic acid dehydrogenation.J Energy Chem2022;68:556-63

[8] Wang H,Li X,Chen J.Activating Pd nanoparticles on sol-gel prepared porous g-C₃N₄/SiO₂ via enlarging the Schottky barrier for efficient dehydrogenation of formic acid.Inorg Chem Front2016;3:1124-9

[9] Li R,Trinh QT.Strong metal-support interaction for 2D materials: application in noble metal/TiB₂ heterointerfaces and their enhanced catalytic performance for formic acid dehydrogenation.Adv Mater2021;33:e2101536

[10] Zhang A,Yao Q.Pd–WO_x heterostructures immobilized by MOFs-derived carbon cage for formic acid dehydrogenation.Appl Catal B2022;309:121278

[11] Barlocco I,Lu X.Disclosing the role of gold on palladium-gold alloyed supported catalysts in formic acid decomposition.ChemCatChem2021;13:4210-22

[12] Wang Z,Meng X,Lian X.Ultrasmall PdAu alloy nanoparticles anchored on amine-functionalized hierarchically porous carbon as additive-free catalysts for highly efficient dehydrogenation of formic acid.Appl Catal B2021;291:120140

[13] Guo B,Lin J.Bimetallic AuPd nanoparticles loaded on amine-functionalized porous boron nitride nanofibers for catalytic dehydrogenation of formic acid.ACS Appl Nano Mater2021;4:1849-57

[14] Wang Z,Mao S,Chen Y.Pd nanoparticles anchored on amino-functionalized hierarchically porous carbon for efficient dehydrogenation of formic acid under ambient conditions.J Mater Chem A2019;7:25791-5

[15] Shao X,Tian F.Amine-functionalized hierarchically porous carbon supported Pd nanocatalysts for highly efficient H₂ generation from formic acid with fast-diffusion channels.J Energy Chem2023;76:249-58

[16] Zhong S,Kitta M.Immobilizing palladium nanoparticles on boron-oxygen-functionalized carbon nanospheres towards efficient hydrogen generation from formic acid.Nano Res2019;12:2966-70

[17] Deng M,Liu Y.Pd nanoparticles confined in pure Silicalite-2 zeolite with enhanced catalytic performance for the dehydrogenation of formic acid at room temperature.Fuel2023;333:126466

[18] Ding R,Li Y,Jia M.Bimetallic PdAu nanoparticles in amine-containing metal–organic framework UiO-66 for catalytic dehydrogenation of formic acid.ACS Appl Nano Mater2021;4:4632-41

[19] Gerber IC.A theory/experience description of support effects in carbon-supported catalysts.Chem Rev2020;120:1250-349

[20] Zhang J,Choksi TS.Strong metal-support interaction boosts activity, selectivity, and stability in electrosynthesis of H₂O₂.J Am Chem Soc2022;144:2255-63

[21] Lin G,Jin Y.Suppressing dissolution of Pt-based electrocatalysts through the electronic metal-support interaction.Adv Energy Mater2021;11:2101050

[22] Li Q,Xie Z.Polar bonds induced strong Pd-support electronic interaction drives remarkably enhanced oxygen reduction activity and stability.Appl Catal B2022;305:121020

[23] Dong Z,Ludwig T.Efficient Pd on carbon catalyst for ammonium formate dehydrogenation: Effect of surface oxygen functional groups.Appl Catal B2023;321:122015

[24] Tang D,Zhang W,Zhang L.Liquid Na/K alloy interfacial synthesis of functional porous carbon at ambient temperature.Angew Chem Int Ed Engl2022;61:e202203967

[25] Luo Y,Xue Y.Electronic structure regulation of iron phthalocyanine induced by anchoring on heteroatom-doping carbon sphere for efficient oxygen reduction reaction and Al-air battery.Small2022;18:e2105594

[26] Yang CL,Yin P.Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells.Science2021;374:459-64

[27] Yu W,Qin Y.The synergistic effect of pyrrolic-N and pyridinic-N with Pt under strong metal-support interaction to achieve high-performance alkaline hydrogen evolution.Adv Energy Mater2022;12:2200110

[28] Yang Y,Shen B.Anchoring nanosized Pd on three-dimensional boron- and nitrogen-codoped graphene aerogels as a highly active multifunctional electrocatalyst for formic acid and methanol oxidation reactions.Inorg Chem Front2020;7:700-8

[29] Yuan J,Mou J.Electrochemically induced amorphous and porous VO_x /N-doped carbon spheres as a cathode for advanced aqueous zinc-ion batteries.Inorg Chem Front2023;10:984-90

[30] Wang Q,Kitta M.Fast dehydrogenation of formic acid over palladium nanoparticles immobilized in nitrogen-doped hierarchically porous carbon.ACS Catal2018;8:12041-5

[31] Yu Y,Liu C,Ge J.Surface interaction between Pd and nitrogen derived from hyperbranched polyamide towards highly effective formic acid dehydrogenation.J Energy Chem2020;40:212-6

[32] Bi QY,Liu YM,Huang FQ.Dehydrogenation of formic acid at room temperature: boosting palladium nanoparticle efficiency by coupling with pyridinic-nitrogen-doped carbon.Angew Chem Int Ed Engl2016;55:11849-53

[33] Deng M,Ma J.Enhanced catalytic performance of n-doped carbon sphere-supported pd nanoparticles by secondary nitrogen source regulation for formic acid dehydrogenation.ACS Appl Mater Interfaces2022;14:18550-60

[34] Ye W,Zou W,Lu R.Controllable synthesis of supported PdAu nanoclusters and their electronic structure-dependent catalytic activity in selective dehydrogenation of formic acid.ACS Appl Mater Interfaces2021;13:34258-65

[35] Zhao X,Xu D,Liu X.Ultrafine PdAg alloy nanoparticles anchored on NH₂-functionalized 2D/2D TiO₂ nanosheet/rGO composite as efficient and reusable catalyst for hydrogen release from additive-free formic acid at room temperature.J Energy Chem2021;59:455-64

[36] Li SJ,Kang X.A simple and effective principle for a rational design of heterogeneous catalysts for dehydrogenation of formic acid.Adv Mater2019;31:e1806781

[37] Masuda S,Futamura Y.PdAg nanoparticles supported on functionalized mesoporous carbon: promotional effect of surface amine groups in reversible hydrogen delivery/storage mediated by formic acid/CO₂.ACS Catal2018;8:2277-85

[38] Ziaee MA,Cui C.Additive-free hydrogen generation from formic acid boosted by amine-functionalized imidazolium-based ionic polymers.ACS Sustainable Chem Eng2018;6:10421-8

[39] Liu B,Song W.Ligand-free noble metal nanocluster catalysts on carbon supports via "soft" nitriding.J Am Chem Soc2016;138:4718-21 PMCID:PMC4852704

[40] Lv H,Guo X,Liu B.Synergistic catalysis of binary RuP nanoclusters on nitrogen-functionalized hollow mesoporous carbon in hydrogen production from the hydrolysis of ammonia borane.J Phys Chem Lett2021;12:696-703

[41] Luo W,Cheng W,Wang Y.A simple and straightforward strategy for synthesis of N,P co-doped porous carbon: an efficient support for Rh nanoparticles for dehydrogenation of ammonia borane and catalytic application.Nanoscale Adv2020;2:1685-93 PMCID:PMC9416816

[42] Yan JM,Yi SS,Zheng WT.Anchoring and upgrading ultrafine NiPd on room-temperature-synthesized bifunctional NH₂-N-rGO toward low-cost and highly efficient catalysts for selective formic acid dehydrogenation.Adv Mater2018;30:e1703038

[43] Li L,Ye Y.Kilogram-scale synthesis and functionalization of carbon dots for superior electrochemical potassium storage.ACS Nano2021;15:6872-85

[44] Duan X,Ding R.Cobalt-doping stabilized active and durable sub-2 nm Pt nanoclusters for low-Pt-loading PEMFC cathode.Adv Energy Mater2022;12:2103144

[45] Ye W,Zhou S.Controlling the synthesis of uniform electron-deficient Pd clusters for superior hydrogen production from formic acid.J Mater Chem A2019;7:10363-71

[46] Chang J,Chang X.Interface synergism and engineering of Pd/Co@N-C for direct ethanol fuel cells.Nat Commun2023;14:1346 PMCID:PMC10008627

[47] Zhao Y,Bodappa N.Elucidating electrochemical CO₂ reduction reaction processes on Cu(hkl) single-crystal surfaces by in situ Raman spectroscopy.Energy Environ Sci2022;15:3968-77

[48] Shan W,Zhao H.In Situ surface-enhanced raman spectroscopic evidence on the origin of selectivity in CO₂ electrocatalytic reduction.ACS Nano2020;14:11363-72

[49] Yu Z,Yang S.Selective dehydrogenation of aqueous formic acid over multifunctional γ-Mo₂N catalysts at a temperature lower than 100 ℃.Appl Catal B2022;313:121445

[50] Zhu H,Du X.Synergistic effect of PtNi alloy loading on TiB₂ to construct SMSI catalysing formic acid dehydrogenation.Sustain Energy Fuels2022;6:5531-8

[51] Li Z,Tsumori N.Tandem nitrogen functionalization of porous carbon: toward immobilizing highly active palladium nanoclusters for dehydrogenation of formic acid.ACS Catal2017;7:2720-4