Multilevel dispersion induced graphdiyne mixed-matrix membranes for ethanol recovery

Abstract

Graphdiyne represents an emerging nanofiller of mixed matrix membranes for high-performance alcohol recovery by pervaporation due to its unique alkyne-rich and porous framework and hydrophobicity. However, such membranes often encounter a persistent challenge of nanofiller agglomeration within the polymer matrix, which diminishes the efficacy of graphdiyne during alcohol recovery. This study proposes a multilevel dispersion strategy that synergistically combines in situ confined growth, ultrasonication, atomization, and rotational shearing throughout membrane preparation to mitigate particle aggregation. The particle agglomeration scale in the polydimethylsiloxane matrix can be effectively reduced from 660 nm of triphenylamine-based graphdiyne to about 291 nm compared to the general stirring-casting method. The mixed matrix membrane loaded with 2.5 wt % triphenylamine-based graphdiyne demonstrated a permeate flux of 2.35 kg·m^–2·h^–1 alongside a separation factor of 11.31 for a 5 wt % ethanol/water solution. Compared to the stirring-casting method, these performances represent enhancements of 41% in permeate flux and 80% in separation factor. Furthermore, a 96 h-continuous pervaporation test indicated the robust stability of the membrane, underscoring the potential for industrial alcohol recovery.

Graphical abstract

Keywords

triphenylamine-based graphdiyne / pervaporation / multilevel dispersion / ethanol recovery / mixed matrix membranes

References

[1] Ning P , Yang G , Hu L , Sun J , Shi L , Zhou Y , Wang Z , Yang J . Recent advances in the valorization of plant biomass. Biotechnology for Biofuels, 2021, 14(1): 102

[2] Sayed E , Wilberforce T , Elsaid K , Rabaia M , Abdelkareem M , Chae K , Olabi A . A critical review on environmental impacts of renewable energy systems and mitigation strategies: wind, hydro, biomass, and geothermal. Science of the Total Environment, 2021, 766: 144505

[3] Wu B , Wang Y , Dai Y , Song C , Zhu Q , Qin H , Tan F , Chen H , Dai L , Hu G . . Current status and future prospective of bio-ethanol industry in China. Renewable & Sustainable Energy Reviews, 2021, 145: 111079

[4] Xie S , Li Z , Luo S , Zhang W . Bioethanol to jet fuel: current status, challenges, and perspectives. Renewable & Sustainable Energy Reviews, 2024, 192: 114240

[5] Peng P , Lan Y , Liang L , Jia K . Membranes for bioethanol production by pervaporation. Biotechnology for Biofuels, 2021, 14(1): 10

[6] Ong Y , Shi G , Le N , Tang Y , Zuo J , Nunes S , Chung T . Recent membrane development for pervaporation processes. Progress in Polymer Science, 2016, 57: 1–31

[7] Zhan X , Zhao X , Gao Z , Ge R , Lu J , Wang L , Li J . Breakthroughs on tailoring membrane materials for ethanol recovery by pervaporation. Chinese Journal of Chemical Engineering, 2022, 52: 19–36

[8] Liu G , Jin W . Pervaporation membrane materials: recent trends and perspectives. Journal of Membrane Science, 2021, 636: 119557

[9] Ahmad A , Li S , Zhao Z . Insight of organic molecule dissolution and diffusion in cross-linked polydimethylsiloxane using molecular simulation. Journal of Membrane Science, 2021, 620: 118863

[10] Pan Y , Hang Y , Zhao X , Liu G , Jin W . Optimizing separation performance and interfacial adhesion of PDMS/PVDF composite membranes for butanol recovery from aqueous solution. Journal of Membrane Science, 2019, 579: 210–218

[11] Cheng X , Pan F , Wang M , Li W , Song Y , Liu G , Yang H , Gao B , Wu H , Jiang Z . Hybrid membranes for pervaporation separations. Journal of Membrane Science, 2017, 541: 329–346

[12] Xue C , Wang Z , Du G , Fan L , Mu Y , Ren J , Bai F . Integration of ethanol removal using carbon nanotube (CNT)-mixed membrane and ethanol fermentation by self-flocculating yeast for antifouling ethanol recovery. Process Biochemistry, 2016, 51(9): 1140–1146

[13] Alberto M , Luque-Alled J , Gao L , Iliut M , Prestat E , Newman L , Haigh S , Vijayaraghavan A , Budd P , Gorgojo P . Enhanced organophilic separations with mixed matrix membranes of polymers of intrinsic microporosity and graphene-like fillers. Journal of Membrane Science, 2017, 526: 437–449

[14] Vane L , Namboodiri V , Meier R . Factors affecting alcohol–water pervaporation performance of hydrophobic zeolite–silicone rubber mixed matrix membranes. Journal of Membrane Science, 2010, 364(1-2): 102–110

[15] Zhuang X , Chen X , Su Y , Luo J , Cao W , Wan Y . Improved performance of PDMS/silicalite-1 pervaporation membranes via designing new silicalite-1 particles. Journal of Membrane Science, 2015, 493: 37–45

[16] Xu S , Zhang H , Yu F , Zhao X , Wang Y . Enhanced ethanol recovery of PDMS mixed matrix membranes with hydrophobically modified ZIF-90. Separation and Purification Technology, 2018, 206: 80–89

[17] Sun Q , He J , Gao L , Lu T , Ma X , Huang C . Synthesis methods of graphdiyne and graphdiyne based materials. Chinese Journal of Chemistry, 2022, 40(7): 872–880

[18] Shandilya P , Mandyal P , Kumar V , Sillanpää M . Properties, synthesis, and recent advancement in photocatalytic applications of graphdiyne: a review. Separation and Purification Technology, 2022, 281: 119825

[19] Sakamoto R , Fukui N , Maeda H , Matsuoka R , Toyoda R , Nishihara H . The accelerating world of graphdiynes. Advanced Materials, 2019, 31(42): 1804211

[20] Cheng S , Liu Z , Yang X , Li C , Fan H , Meng H . Graphdiyne-based integrated membrane for enhanced alcohol-permselective pervaporation. Journal of Membrane Science, 2024, 693: 122397

[21] Li Z , Cheng S , Li X , Li C , Fan H , Meng H . “Kill three birds with one stone”: ultrathin graphdiyne gutter layer-enhanced membrane for ethanol recovery. Journal of Membrane Science, 2025, 718: 123677

[22] Zheng Z , Xue Y , Li Y . A new carbon allotrope: graphdiyne. Trends in Chemistry, 2022, 4(8): 754–768

[23] Jia Z , Li Y , Zuo Z , Liu H , Huang C , Li Y . Synthesis and properties of 2D carbon—graphdiyne. Accounts of Chemical Research, 2017, 50(10): 2470–2478

[24] Gao X , Liu H , Wang D , Zhang J . Graphdiyne: synthesis, properties, and applications. Chemical Society Reviews, 2019, 48(3): 908–936

[25] Zhang T , Wang Y , Yu L , Shi L , Chai S , He C . Graphdiyne: synthesis, modification, and application of a two-dimensional carbonaceous material. New Carbon Materials, 2022, 37(6): 1089–1113

[26] Kim Y , Kim H , Park J , Kim M , Shiori S , Lee J , Jung Y , Yang S . Facile fabrication method of nanocomposite pore filling ion exchange membrane: impregnation method using dispersion solution of inorganic particles. Journal of Membrane Science, 2024, 712: 123241

[27] Park C , Tocci E , Fontananova E , Bahattab M , Aljlil S , Drioli E . Mixed matrix membranes containing functionalized multiwalled carbon nanotubes: mesoscale simulation and experimental approach for optimizing dispersion. Journal of Membrane Science, 2016, 514: 195–209

[28] Al-Hamadani Y , Chu K , Son A , Heo J , Her N , Jang M , Park C , Yoon Y . Stabilization and dispersion of carbon nanomaterials in aqueous solutions: a review. Separation and Purification Technology, 2015, 156: 861–874

[29] Liu Q , Xia X , Xu N , Wang Q , Fan L , Wan Y . Glycerol-assisted uniform dispersion of TpHz nanoparticles in the poly(vinyl alcohol) membrane matrix to construct water permeation channels. Journal of Membrane Science, 2025, 716: 123515

[30] Yang T , Xiao Y , Chung T . Poly-/metal-benzimidazole nano-composite membranes for hydrogen purification. Energy & Environmental Science, 2011, 4(10): 4171–4180

[31] Liu J , Wang N , He F , Bai L , Zhang L , Li Y . Preparation of triphenyl-amine graphdiyne with concomitant assembled morphology and its application for lithium-ion storage. 2D Materials, 2021, 8: 044005

[32] Bai L , Zheng Z , Wang Z , He F , Xue Y , Wang N . Acetylenic bond-driven efficient hydrogen production of a graphdiyne based catalyst. Materials Chemistry Frontiers, 2021, 5(5): 2247–2254

[33] Gascon J , Kapteijn F , Zornoza B , Sebastián V , Casado C , Coronas J . Practical approach to zeolitic membranes and coatings: state of the art, opportunities, barriers, and future perspectives. Chemistry of Materials, 2012, 24(15): 2829–2844

[34] Dong Z , Liu G , Liu S , Liu Z , Jin W . High performance ceramic hollow fiber supported PDMS composite pervaporation membrane for bio-butanol recovery. Journal of Membrane Science, 2014, 450: 38–47

[35] Wang R , Shan L , Zhang G , Ji S . Multiple sprayed composite membranes with high flux for alcohol permselective pervaporation. Journal of Membrane Science, 2013, 432: 33–41

[36] Liu X , Hu D , Li M , Zhang J , Zhu Z , Zeng G , Zhang Y , Sun Y . Preparation and characterization of silicalite-1/PDMS surface sieving pervaporation membrane for separation of ethanol/water mixture. Journal of Applied Polymer Science, 2015, 132(34): 42460

[37] Wang H , Tang S , Ni Y , Zhang C , Zhu X , Zhao Q . Covalent cross-linking for interface engineering of high flux UiO-66-TMS/PDMS pervaporation membranes. Journal of Membrane Science, 2020, 598: 117791

[38] Claes S , Vandezande P , Mullens S , Leysen R , De Sitter K , Andersson A , Maurer F , Van den Rul H , Peeters R , Van Bael M . High flux composite PTMSP-silica nanohybrid membranes for the pervaporation of ethanol/water mixtures. Journal of Membrane Science, 2010, 351(1–2): 160–167

[39] Aroujalian A , Raisi A . Pervaporation as a means of recovering ethanol from lignocellulosic bioconversions. Desalination, 2009, 247(1–3): 509–517

RIGHTS & PERMISSIONS

Higher Education Press