{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,30]],"date-time":"2026-08-30T13:13:01Z","timestamp":1788095581115,"version":"build-2803163510"},"reference-count":57,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2022,2,4]],"date-time":"2022-02-04T00:00:00Z","timestamp":1643932800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>Improper lignocellulosic waste disposal causes severe environmental pollution and health damage. Corn Stover (CS), agricultural, and aseptic packaging, Tetra Pak (TP) cartons, agro-industrial, are two examples of sustainable wastes that are rich in carbohydrate materials and may be used to produce valuable by-products. In addition, attempts were made to enhance cellulose fractionation and improve enzymatic saccharification. In this regard, these two wastes were efficiently employed as substrates for bioethanol production. This research demonstrates the effect of disodium hydrogen phosphate (Na2HPO4) and zinc chloride (ZnCl2) (NZ) as a new catalyst on the development of the sequential pretreatment strategy in the noticeable enzymatic hydrolysis. Physico-chemical changes of the native and the pretreated sustainable wastes were evaluated by compositional analysis, scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). These investigations showed major structural changes after the optimized sequential pretreatment. This pretreatment not only influences the delignification process, but also affects the functionalization of cellulose chemical structure. NZ released a higher glucose concentration (328.8 and 996.8 mg\/dl) than that of ZnCl2 (Z), which released 203.8 and 846.8 mg\/dl from CS and TP, respectively. This work led to the production of about 500 mg\/dl of ethanol, which is promising and a competitor to other studies. These findings contribute to increasing the versatility in the reuse of agricultural and agro-industrial wastes to promote interaction areas of pollution prevention, industrialization, and clean energy production, to attain the keys of sustainable development goals.<\/jats:p>","DOI":"10.3390\/ijms23031777","type":"journal-article","created":{"date-parts":[[2022,2,4]],"date-time":"2022-02-04T11:35:17Z","timestamp":1643974517000},"page":"1777","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":24,"title":["Role of Combined Na2HPO4 and ZnCl2 in the Unprecedented Catalysis of the Sequential Pretreatment of Sustainable Agricultural and Agro-Industrial Wastes in Boosting Bioethanol Production"],"prefix":"10.3390","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3153-7586","authenticated-orcid":false,"given":"Shaimaa","family":"Elyamny","sequence":"first","affiliation":[{"name":"Electronic Materials Research Department, Advanced Technology and New Materials Research Institute (ATNMRI), City of Scientific Research and Technological Applications (SRTA-City), Alexandria 21934, Egypt"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5400-7361","authenticated-orcid":false,"given":"Ali","family":"Hamdy","sequence":"additional","affiliation":[{"name":"Environmental Biotechnology Department, Genetic Engineering and Biotechnology Research Institute (GEBRI), City of Scientific Research and Technological Applications (SRTA-City), Alexandria 21934, Egypt"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0539-382X","authenticated-orcid":false,"given":"Rehab","family":"Ali","sequence":"additional","affiliation":[{"name":"Fabrication Technology Research Department, Advanced Technology and New Materials Research Institute (ATNMRI), City of Scientific Research and Technological Applications (SRTA-City), Alexandria 21934, Egypt"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2434-8904","authenticated-orcid":false,"given":"Hesham","family":"Hamad","sequence":"additional","affiliation":[{"name":"Fabrication Technology Research Department, Advanced Technology and New Materials Research Institute (ATNMRI), City of Scientific Research and Technological Applications (SRTA-City), Alexandria 21934, Egypt"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,2,4]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"111491","DOI":"10.1016\/j.rser.2021.111491","article-title":"Integrating strategies for sustainable conversion of waste biomass into dark-fermentative hydrogen and value-added products","volume":"150","author":"Patel","year":"2021","journal-title":"Renew. Sustain. Energy Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"485","DOI":"10.1002\/bit.25108","article-title":"Investigation of lignin deposition on cellulose during hydrothermal pretreatment, its effect on cellulose hydrolysis, and underlying mechanisms","volume":"111","author":"Li","year":"2014","journal-title":"Biotechnol. Bioeng."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"100011","DOI":"10.1016\/j.ceja.2020.100011","article-title":"Efficient adsorption of organic matters and ions by porous biochar aerogel as pre-treatment of ultrafiltration for shale gas wastewater reuse","volume":"2","author":"Shang","year":"2020","journal-title":"Chem. Eng. J. Adv."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1136","DOI":"10.1016\/j.wasman.2013.01.031","article-title":"Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal\/catalytic tar decomposition","volume":"33","author":"Haydary","year":"2013","journal-title":"Waste Manag."},{"key":"ref_5","unstructured":"Tetra Pak (2021, December 09). Tetra Pak in Figures (2021). Available online: www.tetrapak.com\/mx\/about\/facts-figures."},{"key":"ref_6","unstructured":"Tetra Pak (2021, December 09). Post-Consumer Recycling (2019). Available online: https:\/\/www.tetrapak.com\/us\/sustainability\/recycling."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"124550","DOI":"10.1016\/j.biortech.2020.124550","article-title":"Integrating anaerobic digestion of potato peels to methanol production by methanotrophs immobilized on banana leaves","volume":"323","author":"Patel","year":"2021","journal-title":"Bioresour. Technol."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"37","DOI":"10.1016\/S0960-8524(01)00118-3","article-title":"Energy production from biomass (Part 1): Overview of biomass","volume":"83","author":"McKendry","year":"2002","journal-title":"Bioresour. Technol."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"5032","DOI":"10.1016\/j.jece.2018.07.043","article-title":"Physicochemical properties of new cellulose-TiO2 composites for the removal of water pollutants: Developing specific interactions and performances by cellulose functionalization","volume":"6","author":"Hamad","year":"2018","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"550","DOI":"10.1016\/j.rser.2014.08.032","article-title":"Sustainable bio-ethanol production from agro-residues: A review","volume":"41","author":"Gupta","year":"2015","journal-title":"Renew. Sustain. Energy Rev."},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Hamdy, A., Elhafez, S.A., Hamad, H., and Ali, R. (2021). The interplay of autoclaving with oxalate as pretreatment technique in the view of bioethanol production based on corn stover. Polymers, 13.","DOI":"10.3390\/polym13213762"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"196","DOI":"10.1016\/j.fuproc.2016.12.007","article-title":"A review on the pretreatment of lignocellulose for high-value chemicals","volume":"160","author":"Chen","year":"2017","journal-title":"Fuel Process. Technol."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"117457","DOI":"10.1016\/j.energy.2020.117457","article-title":"Different pretreatment technologies of lignocellulosic biomass for bioethanol production: An overview","volume":"199","author":"Rezania","year":"2020","journal-title":"Energy"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"209","DOI":"10.1016\/j.biortech.2016.06.063","article-title":"combined sodium phosphate and sodium sulphide pretreatment for enhanced enzymatic digestibility and delignification of corn stover","volume":"218","author":"Qing","year":"2016","journal-title":"Bioresour. Technol."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1321","DOI":"10.1016\/j.carbpol.2012.10.019","article-title":"Effects of NH4Cl and MgCl2 on pretreatment and xylan hydrolysis of Miscanthus straw","volume":"92","author":"Kang","year":"2013","journal-title":"Carbohydr. Polym."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"455","DOI":"10.1016\/j.ultsonch.2015.10.017","article-title":"Pretreatment combining ultrasound and sodium percarbonate under mild conditions for efficient degradation of corn stover","volume":"29","author":"Nakashima","year":"2016","journal-title":"Ultrason. Sonochem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"105574","DOI":"10.1016\/j.biombioe.2020.105574","article-title":"Process development for sodium carbonate pretreatment and enzymatic saccharification of rice straw for bioethanol production","volume":"138","author":"Singh","year":"2020","journal-title":"Biomass Bioenergy"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"42","DOI":"10.1016\/j.biortech.2015.08.085","article-title":"A review on alkaline pretreatment technology for bioconversion of lignocellulosic biomass","volume":"199","author":"Kim","year":"2016","journal-title":"Bioresour. Technol."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"63","DOI":"10.1016\/j.biortech.2014.03.024","article-title":"Comparison of sodium carbonate-oxygen and sodium-hydroxide oxygen pretreatments on the chemical composition and enzymatic saccharafication of wheat straw","volume":"161","author":"Geng","year":"2014","journal-title":"Bioresour. Technol."},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Hamad, H., Castelo-Quib\u00e9n, J., Morales-Torres, S., Carrasco-Mar\u00edn, F., P\u00e9rez-Cadenas, A.F., and Maldonado, F.J. (2018). On the interactions and synergism between phases of carbon-phosphorus-titanium composites synthetized from cellulose for the removal of the orange-G dye. Materials, 11.","DOI":"10.3390\/ma11091766"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"35","DOI":"10.1016\/j.biortech.2017.03.031","article-title":"Microwave-assisted inorganic salt pretreatment of sugarcane leaf waste: Effect on physiochemical structure and enzymatic saccharification","volume":"235","author":"Moodley","year":"2017","journal-title":"Bioresour. Technol."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"3818","DOI":"10.1039\/D1GC00376C","article-title":"Metal phosphate catalysts to upgrade lignocellulose biomass into value-added chemicals and biofuels","volume":"23","author":"Shivhare","year":"2021","journal-title":"Green Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"8349","DOI":"10.1021\/acs.jafc.5b01813","article-title":"Recent advances in the application of inorganic salt pretreatment for transforming lignocellulosic biomass into reducing sugars","volume":"63","author":"Loow","year":"2015","journal-title":"J. Agric. Food Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"123372","DOI":"10.1016\/j.biortech.2020.123372","article-title":"Progress in the development of alkali and metal salt catalysed lignocellulosic pretreatment regimes: Potential for bioethanol production","volume":"310","author":"Moodley","year":"2020","journal-title":"Bioresour. Technol."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1833","DOI":"10.1016\/j.biombioe.2011.01.014","article-title":"Organosolv pretreatment of Liriodendron tulipifera and simultaneous saccharification and fermentation for bioethanol production","volume":"35","author":"Koo","year":"2011","journal-title":"Biomass Bioenergy"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1479","DOI":"10.1016\/j.renene.2020.02.111","article-title":"The effect of using different acids to catalyze the prehydrolysis stage on the organosolv delignification of beech wood in two-stage process","volume":"153","author":"Ibrahim","year":"2020","journal-title":"Renew. Energy"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"13576","DOI":"10.1021\/acssuschemeng.0c03492","article-title":"Partial amorphization of cellulose through zinc chloride treatment: A facile and sustainable pathway to functional cellulose nanofibers with flame-retardant and catalytic properties","volume":"8","author":"Burger","year":"2020","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"122432","DOI":"10.1016\/j.biortech.2019.122432","article-title":"A review on high catalytic efficiency of solid acid catalysts for lignin valorization","volume":"298","author":"Guan","year":"2020","journal-title":"Bioresour. Technol."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"116552","DOI":"10.1016\/j.fuel.2019.116552","article-title":"Valorization of sugarcane bagasse for bioethanol production through simultaneous saccharification and fermentation: Optimization and kinetic studies","volume":"262","author":"Jugwanth","year":"2020","journal-title":"Fuel"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"4992","DOI":"10.1016\/j.biortech.2009.11.007","article-title":"Woody biomass pretreatment for cellulosic ethanol production: Technology and energy consumption evaluation","volume":"101","author":"Zhu","year":"2010","journal-title":"Bioresour. Technol."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"120","DOI":"10.1016\/j.enconman.2016.06.022","article-title":"Optimization of twin gear-based pretreatment of rice straw for bioethanol production","volume":"141","author":"Ahmed","year":"2017","journal-title":"Energy Convers. Manag."},{"key":"ref_32","first-page":"50","article-title":"Enhancement of bio-ethanol production potential of wheat straw by reducing furfural and 5-hydroxymethylfurfural (HMF)","volume":"4","author":"Prasad","year":"2018","journal-title":"Bioresour. Technol."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"318","DOI":"10.1016\/j.biortech.2019.01.068","article-title":"Microwave-assisted pretreatment of maize distillery stillage with the use of dilute sulfuric acid in the production of cellulosic ethanol","volume":"278","author":"Mikulski","year":"2019","journal-title":"Bioresour. Technol."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"160","DOI":"10.1016\/j.biortech.2013.01.012","article-title":"Effects of inorganic salts on pretreatment of Miscanthus straw","volume":"132","author":"Kang","year":"2013","journal-title":"Bioresour. Technol."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"317","DOI":"10.1016\/j.ecoleng.2016.03.015","article-title":"Potential of using green adsorbent of heavy metal removal fromaqueous solutions: Adsorption kinetics, isotherm, thermodynamic, mechanism and economic analysis","volume":"91","author":"Ali","year":"2016","journal-title":"Ecol. Eng."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"242","DOI":"10.1080\/00986445.2019.1705797","article-title":"Enhancement of biogas production via green ZnO nanoparticles: Experimental results of selected herbaceous crops","volume":"208","author":"Hassaan","year":"2021","journal-title":"Chem. Eng. Commun."},{"key":"ref_37","first-page":"16051","article-title":"Journey from ceramic waste to highly efficient toxic dye adsorption from aqueous solutions via one-pot synthesis of CaSO4 rod-shape with silica","volume":"6","author":"Hamad","year":"2020","journal-title":"J. Mater. Res. Technol."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"117297","DOI":"10.1016\/j.fuel.2020.117297","article-title":"Highly active and stable magnetically recyclable CuFe2O4 as a heterogenous catalyst for efficient conversion of waste frying oil to biodiesel","volume":"268","author":"Ali","year":"2020","journal-title":"Fuel"},{"key":"ref_39","first-page":"1161","article-title":"Highly crystalline heterogeneous catalyst synthesis from industrial waste for sustainable biodiesel production","volume":"63","author":"Ali","year":"2020","journal-title":"Egypt. J. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"1081","DOI":"10.1007\/s13197-020-04622-z","article-title":"Upgrading of agro-industrial green biomass residues from chocolate industry for adsorption process: Diffusion and mechanistic insights","volume":"58","author":"Hamadi","year":"2021","journal-title":"J. Food Sci. Technol."},{"key":"ref_41","first-page":"1443","article-title":"Photocatalytic degradation of reactive black 5 using photo-fenton and ZnO nanoparticles under UV irradiation","volume":"63","author":"Hassaan","year":"2020","journal-title":"Egypt. J. Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"407","DOI":"10.1016\/j.indcrop.2017.10.029","article-title":"Smart utilization of jatropha (Jatropha curcas Linnaeus) seeds for biodiesel production: Optimization and mechanism","volume":"111","author":"Kamel","year":"2018","journal-title":"Ind. Crop. Prod."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1313","DOI":"10.1016\/j.ijbiomac.2019.10.176","article-title":"Electrospun cellulose acetate nanofiber incorporated with hydroxyapatite for removal of heavy metals","volume":"151","author":"Hamad","year":"2020","journal-title":"Int. J. Biol. Macromol."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"103998","DOI":"10.1016\/j.microc.2019.103998","article-title":"Fabrication and characterization of electrospun Fe3O4\/o-MWCNTs\/polyamide 6 hybrid nanofibrous membrane composite as an efficient and recoverable adsorbent for removal of Pb (II)","volume":"149","author":"Bassyouni","year":"2019","journal-title":"Microchem. J."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"17900","DOI":"10.1021\/ie402791m","article-title":"Preparation and characterization of novel regenerated cellulose films via sol\u2212gel technology","volume":"52","author":"Zhu","year":"2013","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"7790","DOI":"10.1038\/s41598-021-87363-z","article-title":"Unveiling the role of novel biogenic functionalized CuFe hybrid nanocomposites in boosting anticancer, antimicrobial and biosorption activities","volume":"11","author":"Eltarahony","year":"2021","journal-title":"Sci. Rep."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"5967","DOI":"10.1016\/j.ceramint.2015.01.033","article-title":"A novel hydroxyapatite\u2014Hardystonite nanocomposite ceramic","volume":"41","author":"Gheisari","year":"2015","journal-title":"Ceram. Int."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"5806","DOI":"10.1021\/jf0605392","article-title":"Organosolv ethanol lignin from hybrid poplar as a radical scavenger: Relationship between lignin structure, extraction conditions, and antioxidant activity","volume":"54","author":"Pan","year":"2006","journal-title":"J. Agric. Food Chem."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"822","DOI":"10.1016\/j.jscs.2016.01.001","article-title":"Preparation and characterization of carbons from \u03b2-cyclodextrin dehydration and from olive pomace activation and their application for boron adsorption","volume":"21","author":"Jaouadi","year":"2017","journal-title":"J. Saudi Chem. Soc."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"41","DOI":"10.1007\/s12649-016-9585-2","article-title":"Isolation of nanocrystalline cellulose: A technological route for valorizing recycled tetra pak aseptic multilayered food packaging wastes","volume":"8","author":"Diop","year":"2017","journal-title":"Waste Biomass Valoriz."},{"key":"ref_51","doi-asserted-by":"crossref","unstructured":"Hamad, H., Bail\u00f3n-Garc\u00eda, E., Morales-Torres, S., Carrasco-Mar\u00edn, F., P\u00e9rez-Cadenas, A.F., and Maldonado-H\u00f3dar, F.J. (2020). Functionalized cellulose for the controlled synthesis of novel carbon\u2013Ti nanocomposites: Physicochemical and photocatalytic properties. Nanomaterials, 10.","DOI":"10.3390\/nano10040729"},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"202","DOI":"10.1016\/j.biortech.2015.08.062","article-title":"Development of a novel sequential pretreatment strategy for the production of bioethanol from sugarcane trash","volume":"199","author":"Raghavi","year":"2016","journal-title":"Bioresour. Technol."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"105454","DOI":"10.1016\/j.biombioe.2019.105454","article-title":"Optimization of an organosolv method using glycerol with iron catalysts for the pretreatment of water hyacinth","volume":"133","author":"Santana","year":"2020","journal-title":"Biomass Bioenergy"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"1494","DOI":"10.1002\/jctb.2455","article-title":"Ethanosolv pretreatment of barley straw with iron (III) chloride for enzymatic saccharification","volume":"85","author":"Kim","year":"2010","journal-title":"J. Chem. Technol. Biotechnol."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"426","DOI":"10.1021\/ac60147a030","article-title":"Use of dinitrosalicylic acid reagent for determination of reducing sugar","volume":"31","author":"Miller","year":"1959","journal-title":"Anal. Chem."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"3583","DOI":"10.3168\/jds.S0022-0302(91)78551-2","article-title":"Methods for Dietary Fiber, Neutral Detergent Fiber, and Nonstarch Polysaccharides in Relation to Animal Nutrition","volume":"74","author":"Robertson","year":"1991","journal-title":"J. Dairy Sci."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"145","DOI":"10.1016\/S0008-6223(01)00165-8","article-title":"Surface oxides on carbon and their analysis: A critical assessment","volume":"40","author":"Boehm","year":"2002","journal-title":"Carbon"}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/23\/3\/1777\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T22:14:01Z","timestamp":1760134441000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/23\/3\/1777"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,2,4]]},"references-count":57,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2022,2]]}},"alternative-id":["ijms23031777"],"URL":"https:\/\/doi.org\/10.3390\/ijms23031777","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,2,4]]}}}