成型沸石的银后修饰策略用于痕量乙烯捕获

doi:10.11949/0438-1157.20251025

摘要/Abstract

摘要：

乙烯是加速果蔬衰败的关键激素，高效去除痕量乙烯对果蔬采后保鲜至关重要。本研究突破传统粉末吸附剂先改性后成型方式导致的活性位点易损与孔道堵塞问题，提出成型吸附剂温和后改性策略，以市售silicalite-1球形颗粒为基体，通过温和后处理银修饰，在保持球形颗粒完整性的同时，成功制备系列银负载吸附剂S-Ag-X。适量银负载的S-Ag-β在超低分压下的乙烯吸附量约为silicalite-1的15倍，并表现出更高的C₂H₄/CO₂和C₂H₄/N₂选择性。穿透实验表明，该材料在高湿和复杂气氛中仍具有优异乙烯吸附性能和循环稳定性。香蕉贮藏实验也验证了其可有效延长水果保质期。本研究为粉末吸附剂实际应用中的成型与性能兼顾难题提供了有效解决方案，具有较强的实际应用价值。

关键词: 沸石, Silicalite-1, 银改性, 吸附剂, 乙烯吸附, 水果保鲜

Abstract:

Ethylene is a key hormone that accelerates the spoilage of fruits and vegetables. Efficient removal of trace ethylene is crucial for postharvest preservation. This study overcomes the challenges of vulnerable active sites and pore blockage associated with the conventional method of modifying powdered adsorbents before shaping. Instead, we propose a mild post-modification strategy for shaped adsorbents. Using commercially available silicalite-1 spherical beads as the substrate, a series of silver-loaded adsorbents, denoted as S-Ag-X, were successfully prepared through a gentle silver decoration post-treatment. This method preserved the integrity of the spherical particles. The adsorbent S-Ag-β with an optimal silver loading exhibited an ethylene adsorption capacity approximately 15 times higher than that of pure silicalite-1 at ultra-low partial pressures, along with superior selectivity for C₂H₄/CO₂ and C₂H₄/N₂. Breakthrough experiments demonstrated that the material maintains excellent ethylene adsorption performance and cycling stability even under high humidity and in complex gas atmospheres. Banana storage tests further confirmed its effectiveness in extending fruit shelf life. This research provides an effective solution to the longstanding challenge of balancing shaping and performance for powdered adsorbents in practical applications, demonstrating significant practical value.

Key words: zeolite, silicalite-1, Ag-modification, adsorbents, ethylene adsorption, fruit preservation

中图分类号:

TQ 028.8

任永恒, 王猛, 杨江峰, 陈杨, 李晋平, 李立博. 成型沸石的银后修饰策略用于痕量乙烯捕获[J]. 化工学报, DOI: 10.11949/0438-1157.20251025.

Yongheng REN, Meng WANG, Jiangfeng YANG, Yang CHEN, Jinping LI, Libo LI. Silver post-modification strategy of shaped zeolites for trace ethylene capture[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251025.

图/表 8

图1 球形Silicalite-1后处理银改性用于水果保鲜的示意图。

Fig.1 Schematic diagram of spherical Silicalite-1 post-treated with silver modification for fruit preservation.

表1 ICP测定的S-Ag-X中的银含量

Table 1 Data of silver content in S-Ag-X measured by ICP

	测定的Ag浓度/（mg/L）	计算的Ag含量/wt%
S-1	-	-
S-Ag-α	1.938	0.48
S-Ag-β	4.405	1.10
S-Ag-γ	6.121	1.53
S-Ag-δ	8.743	2.19

图2 S-1和S-Ag-X的XRD及77K下的N2吸脱附等温线

Fig.2 PXRD and N2 adsorption-desorption isotherms at 77 K of S-1 and S-Ag-X

图3 (a，b)S-1和不同Ag含量的S-Ag-X在298 K下的C2H4吸附等温线。

Fig.3 (a, b) C2H4 adsorption isotherms of S-1 and S-Ag-X with different Ag contents at 298 K.

图4 (a)S-1和(b)S-Ag在273 K，298 K和313 K下的C2H4吸附等温线以及(c)计算的C2H4吸附热

Fig.4 C2H4 adsorption isotherms of (a) S-1 and (b) S-Ag at 273 K, 298 K, and 313 K, and (c) calculated C2H4 adsorption heat

图5 (a)S-1和(b)S-Ag-β在298K下的C2H4，CO2，N2和H2O的单组分吸附等温线。S-1和S-Ag-β在298K下的(c)C2H4/CO2（10/90，v/v）和(d)C2H4/N2（0.1/99.9，v/v）的IAST选择性

Fig.5 (a) S-1 and (b) S-Ag-β single-component adsorption isotherms of C2H4, CO2, N2, and H2O at 298 K. IAST selectivity of S-1 and S-Ag-β at 298 K for (c) C2H4/CO2 (10/90, v/v) and (d) C2H4/N2 (0.1/99.9, v/v)

图6 (a)在298 K和1 bar下S-1和S-Ag-β的C2H4/N2（0.1/99.9，v/v）穿透曲线对比；在298 K和1 bar下，S-Ag-β对于(b)干燥和(c)潮湿的C2H4/CO2/N2（0.1/1/98.9，v/v/v）三组分穿透曲线；(d)S-Ag-β潮湿条件下的三组分穿透循环

Fig.6 (a) Comparison of C2H4/N2 (0.1/99.9, v/v) breakthrough curves for S-1 and S-Ag-β at 298 K and 1 bar; breakthrough curves of S-Ag-β for (b) dry and (c) humid C2H4/CO2/N2 (0.1/1/98.9, v/v/v) mixed gas; (d) breakthrough cycle tests of S-Ag-β under humid conditions

图7 不同时间间隔的香蕉变化过程

Fig.7 The process of banana changes at different time intervals

参考文献 52

[1]	Kepinski S, Leyser O. SCF-mediated proteolysis and negative regulation in ethylene signaling[J]. Cell, 2003, 115(6): 647-648.
[2]	Keller N, Ducamp M N, Robert D, et al. Ethylene removal and fresh product storage: a challenge at the frontiers of chemistry. toward an approach by photocatalytic oxidation[J]. Chemical Reviews, 2013, 113(7): 5029-5070.
[3]	Burg S P, Burg E A. Ethylene action and the ripening of fruits[J]. Science, 1965, 148(3674): 1190-1196.
[4]	Pathak N, Caleb O J, Geyer M, et al. Photocatalytic and photochemical oxidation of ethylene: potential for storage of fresh produce—a review[J]. Food and Bioprocess Technology, 2017, 10(6): 982-1001.
[5]	Mwelase S, Adeyemi J O, Fawole O A. Recent advances in postharvest application of exogenous phytohormones for quality preservation of fruits and vegetables[J]. Plants, 2024, 13(22): 3255.
[6]	Jiang Y, Liu Z P, Peydayesh M, et al. Ethylene control in fruit quality assurance: a material science perspective[J]. Aggregate, 2024, 5(5): e565.
[7]	Sadeghi K, Lee Y, Seo J. Ethylene scavenging systems in packaging of fresh produce: a review[J]. Food Reviews International, 2021, 37(2): 155-176.
[8]	Xie J W, Situ W, Wang R, et al. The visible light photocatalytic degradation of ethylene using a polyvinyl alcohol film loaded with Ag₂O-TiO₂-Bi₂WO₆ heterojunction microspheres[J]. Applied Surface Science, 2022, 584: 152562.
[9]	Chen L Z, Xie X T, Song X L, et al. Photocatalytic degradation of ethylene in cold storage using the nanocomposite photocatalyst MIL101(Fe)-TiO₂-rGO[J]. Chemical Engineering Journal, 2021, 424: 130407.
[10]	Nielsen M G, Vesborg P C K, Hansen O, et al. Removal of low concentration contaminant species using photocatalysis: Elimination of ethene to sub-ppm levels with and without water vapor present[J]. Chemical Engineering Journal, 2015, 262: 648-657.
[11]	Soares T R P, Reis A F, dos Santos J W S, et al. NaY-Ag zeolite chitosan coating kraft paper applied as ethylene scavenger packaging[J]. Food and Bioprocess Technology, 2023, 16(5): 1101-1115.
[12]	Dziedzic E, Błaszczyk J, Bieniasz M, et al. Effect of modified (MAP) and controlled atmosphere (CA) storage on the quality and bioactive compounds of blue honeysuckle fruits (Lonicera caerulea L.)[J]. Scientia Horticulturae, 2020, 265: 109226.
[13]	Cheng J H, Chen M, Sun D W. Ethylene synergism control using integrated cold plasma technologies to enhance fruit and vegetable quality[J]. Food Engineering Reviews, 2025, 17(1): 55-74.
[14]	Álvarez-Hernández M H, Artés-Hernández F, Ávalos-Belmontes F, et al. Current scenario of adsorbent materials used in ethylene scavenging systems to extend fruit and vegetable postharvest life[J]. Food and Bioprocess Technology, 2018, 11(3): 511-525.
[15]	Álvarez-Hernández M H, Martínez-Hernández G B, Avalos-Belmontes F, et al. Potassium permanganate-based ethylene scavengers for fresh horticultural produce as an active packaging[J]. Food Engineering Reviews, 2019, 11(3): 159-183.
[16]	Wang Y N, Xu J F, Iskakov R M, et al. Ethylene scavengers for extended freshness: a critical comparison between physisorption and chemistry process[J]. Applied Food Research, 2025, 5(2): 101267.
[17]	Lin R B, Li L B, Zhou H L, et al. Molecular sieving of ethylene from ethane using a rigid metal–organic framework[J]. Nature Materials, 2018, 17(12): 1128-1133.
[18]	王涛虹, 王超, 李政, 等. 固载Cu(Ⅰ)的π络合MOF吸附剂用于乙烷/乙烯的选择性分离[J]. 化工学报, 2024, 75(7): 2565-2573.
	Wang T H, Wang C, Li Z, et al. Immobilize Cu(Ⅰ) into π-complexed MOF adsorbent for selectivity separation of ethane/ethylene[J]. CIESC Journal, 2024, 75(7): 2565-2573.
[19]	Chen F Q, Ding J Q, Guo K Q, et al. CoNi alloy nanoparticles embedded in metal–organic framework-derived carbon for the highly efficient separation of xenon and krypton via a charge-transfer effect[J]. Angewandte Chemie International Edition, 2021, 60(5): 2431-2438.
[20]	Li L B, Lin R B, Krishna R, et al. Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites[J]. Science, 2018, 362(6413): 443-446.
[21]	Chen Y, Wu Z D, Fan L L, et al. Direct ethylene purification from cracking gas via a metal–organic framework through pore geometry fitting[J]. Engineering, 2024, 41: 84-92.
[22]	Jiang Y C, Luo M F, Niu Z N, et al. In-situ growth of bimetallic FeCo-MOF on magnetic biochar for enhanced clearance of tetracycline and fruit preservation[J]. Chemical Engineering Journal, 2023, 451: 138804.
[23]	Li Y P, Zhao Y N, Li S N, et al. Ultrahigh-uptake capacity-enabled gas separation and fruit preservation by a new single-walled nickel–organic framework[J]. Advanced Science, 2021, 8(12): 2003141.
[24]	Kumar A, Gupta V, Singh S, et al. Pine needles lignocellulosic ethylene scavenging paper impregnated with nanozeolite for active packaging applications[J]. Industrial Crops and Products, 2021, 170: 113752.
[25]	王恺华, 陈杨, 王毅, 等. 基于多氮唑配体制备金属有机框架用于乙炔吸附分离[J]. 科学通报, 2024, 69(16): 2278-2287.
	Wang K H, Chen Y, Wang Y, et al. Synthesis of metal organic frameworks based on multiazole ligands for adsorption and separation of acetylene[J]. Chinese Science Bulletin, 2024, 69(16): 2278-2287.
[26]	Zhang L, Wang Y, Chen Y, et al. Metal-organic frameworks for ethane-selective adsorption: a comprehensive review on structural design and separation applications[J]. Coordination Chemistry Reviews, 2025, 544: 216974.
[27]	Chopra S, Dhumal S, Abeli P, et al. Metal-organic frameworks have utility in adsorption and release of ethylene and 1-methylcyclopropene in fresh produce packaging[J]. Postharvest Biology and Technology, 2017, 130: 48-55.
[28]	Nian L Y, Wang M J, Wang F F, et al. Multifunctional material Cer@MHKUST-1 with efficient preservation capability[J]. Chemical Engineering Journal, 2022, 433: 133267.
[29]	An Y, Lv X L, Jiang W Y, et al. The stability of MOFs in aqueous solutions—research progress and prospects[J]. Green Chemical Engineering, 2024, 5(2): 187-204.
[30]	Li Y, Yu J H. New stories of zeolite structures: their descriptions, determinations, predictions, and evaluations[J]. Chemical Reviews, 2014, 114(14): 7268-7316.
[31]	Ren Y H, Chen Y, Chen H W, et al. Electrostatically driven kinetic inverse CO₂/C₂H₂ separation in LTA-type zeolites[J]. Chinese Journal of Structural Chemistry, 2024, 43(10): 100394.
[32]	陈彰旭, 姜伟, 陈志彬, 等. 壳聚糖复合物在水果保鲜中的应用研究进展[J]. 化工进展, 2011, 30(12): 2724-2727.
	Chen Z X, Jiang W, Chen Z B, et al. Progress in application studies of chitosan complex on fruit refreshing[J]. Chemical Industry and Engineering Progress, 2011, 30(12): 2724-2727.
[33]	Gueibe C, Rutten J, Camps J, et al. Silver-exchanged zeolites for collecting and separating xenon directly from atmospheric air[J]. Separation and Purification Technology, 2023, 323: 124433.
[34]	Li Y X, Shen J X, Peng S S, et al. Enhancing oxidation resistance of Cu(I) by tailoring microenvironment in zeolites for efficient adsorptive desulfurization[J]. Nature Communications, 2020, 11: 3206.
[35]	Qi Y, Yang H M, Li C L, et al. Trace ethylene adsorbents Ag/F-Z5(X) for improved preservation of fruits and vegetables: Enhanced adsorption and water resistance[J]. Separation and Purification Technology, 2024, 347: 127634.
[36]	Ferreira R, Lopes H, Lourenço J P, et al. Ethylene removal by Ag-based ZSM-5 adsorbents for the preservation of climacteric fruits[J]. Microporous and Mesoporous Materials, 2024, 370: 113055.
[37]	Ren Y H, Liu X H, Dai G G, et al. Smooth pore surface in zeolites for krypton capture under humid conditions[J]. Green Chemical Engineering, 2025, 6(4): 431-438.
[38]	Ren Y H, Chen Y, Yang J F, et al. In-situ silver-modification of Silicalite-1 for trace ethylene capture under humid conditions[J]. Applied Surface Science, 2023, 613: 156002.
[39]	Wang H, Liu Y T, Ren Y H, et al. Hydrophobic Silicalite-1@Ag⁺ based MMM for C₂H₄/C₂H₆ separation under long-period humid conditions[J]. Journal of Membrane Science, 2024, 696: 122521.
[40]	van Zandvoort I, van Klink G P M, de Jong E, et al. Selectivity and stability of zeolites [Ca] A and [Ag] A towards ethylene adsorption and desorption from complex gas mixtures[J]. Microporous and Mesoporous Materials, 2018, 263: 142-149.
[41]	Li Y H, Min X B, Li W H, et al. Experimental and computational evaluation of Ag-exchanged ZSM-5 and SSZ-13 for xenon capture[J]. Microporous and Mesoporous Materials, 2022, 330: 111631.
[42]	尚华, 白洪灏, 刘佳奇, 等. CH₄-N₂在自支撑颗粒型Silicalite-1上的吸附分离及PSA模拟[J]. 化工学报, 2020, 71(5): 2088-2098.
	Shang H, Bai H H, Liu J Q, et al. PSA simulation and adsorption separation of CH₄-N₂ by self-supporting pellets Silicalite-1[J]. CIESC Journal, 2020, 71(5): 2088-2098.
[43]	Xiong Y, Tian T, L'Hermitte A, et al. Using silver exchange to achieve high uptake and selectivity for propylene/propane separation in zeolite Y[J]. Chemical Engineering Journal, 2022, 446: 137104.
[44]	Zhang H D, Wang Z W, Wang W D, et al. One-pot synthesis of Ag@silicalite-1 using different silver amine complexes and their performance for styrene oxidation[J]. New Journal of Chemistry, 2021, 45(45): 21293-21298.
[45]	Liu C W, Xin M D, Wang C L, et al. Ag₂O nanoparticles encapsulated in Ag-exchanged LTA zeolites for highly selective separation of ethylene/ethane[J]. ACS Applied Nano Materials, 2023, 6(7): 5374-5383.
[46]	Li B Y, Zhang Y M, Krishna R, et al. Introduction of π-complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane[J]. Journal of the American Chemical Society, 2014, 136(24): 8654-8660.
[47]	Trinh Q H, Lee S B, Mok Y S. Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite[J]. Journal of Hazardous Materials, 2015, 285: 525-534.
[48]	Uchida S, Kawamoto R, Tagami H, et al. Highly selective sorption of small unsaturated hydrocarbons by nonporous flexible framework with silver ion[J]. Journal of the American Chemical Society, 2008, 130(37): 12370-12376.
[49]	Monzón J D, Pereyra A M, Gonzalez M R, et al. Ethylene adsorption onto thermally treated AgA-Zeolite[J]. Applied Surface Science, 2021, 542: 148748.
[50]	Yang R T, Kikkinides E S. New sorbents for olefin/paraffin separations by adsorption via π-complexation[J]. AIChE Journal, 1995, 41(3): 509-517.
[51]	Evans H A, Mullangi D, Deng Z Y, et al. Aluminum formate, Al(HCOO)₃: an earth-abundant, scalable, and highly selective material for CO₂ capture[J]. Science Advances, 2022, 8(44): eade1473.
[52]	Liu S S, Chen Y L, Yue B, et al. Cascade adsorptive separation of light hydrocarbons by commercial zeolites[J]. Journal of Energy Chemistry, 2022, 72: 299-305.