{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,29]],"date-time":"2026-07-29T22:06:12Z","timestamp":1785362772033,"version":"3.55.0"},"reference-count":47,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2019,9,11]],"date-time":"2019-09-11T00:00:00Z","timestamp":1568160000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Nanomaterials"],"abstract":"<jats:p>Composite nanomaterials have been widely used in catalysis because of their attractive properties and various functions. Among them, the preparation of composite nanomaterials by redox has attracted much attention. In this work, pure Cu2O was prepared by liquid phase reduction with Cu(NO3)2 as the copper source, NaOH as a precipitator, and sodium ascorbate as the reductant. With Fe(NO3)3 as the iron source and solid-state phase reaction between Fe3+ and Cu2O, CuxO-FeyOz nanocatalysts with different Fe\/Cu ratios were prepared. The effects of the Fe\/Cu ratio on the structure of CuxO-FeyOz nanocatalysts were studied by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet confocal Raman (Raman), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS, XAES), and hydrogen temperature-programmed reduction (H2-TPR). Furthermore, the structure\u2013activity relationship between the structure of CuxO-FeyOz nanocatalysts and the performance of formaldehyde ethynylation was discussed. The results show that Fe3+ deposited preferentially on the edges and corners of the Cu2O surface, and a redox reaction between Fe3+ and Cu+ occurred, forming CuxO-FeyOz nanoparticles containing Cu+, Cu2+, Fe2+, and Fe3+. With the increase of the Fe\/Cu ratio, the content of CuxO-FeyOz increased. When the Fe\/Cu ratio reached 0.8, a core\u2013shell structure with Cu2O inside and a CuxO-FeyOz coating on the outside was formed. Because of the large physical surface area and the heterogeneous structure formed by CuxO-FeyOz, the formation of nonactive Cu metal is inhibited, and the most active species of Cu+ are exposed on the surface, showing the best formaldehyde ethynylation activity.<\/jats:p>","DOI":"10.3390\/nano9091301","type":"journal-article","created":{"date-parts":[[2019,9,11]],"date-time":"2019-09-11T11:26:34Z","timestamp":1568201194000},"page":"1301","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":27,"title":["Application of CuxO-FeyOz Nanocatalysts in Ethynylation of Formaldehyde"],"prefix":"10.3390","volume":"9","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3740-571X","authenticated-orcid":false,"given":"Haitao","family":"Li","sequence":"first","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lijun","family":"Ban","sequence":"additional","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhuzhu","family":"Niu","sequence":"additional","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xin","family":"Huang","sequence":"additional","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pingfan","family":"Meng","sequence":"additional","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xudong","family":"Han","sequence":"additional","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yin","family":"Zhang","sequence":"additional","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongxi","family":"Zhang","sequence":"additional","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yongxiang","family":"Zhao","sequence":"additional","affiliation":[{"name":"Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2019,9,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1145","DOI":"10.1007\/s11244-010-9550-4","article-title":"Selective hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol over particulate Raney\u00ae nickel catalysts","volume":"53","author":"Tanielyan","year":"2010","journal-title":"Top. Catal."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"441","DOI":"10.1016\/j.catcom.2007.07.023","article-title":"Hydrogenation activity and selectivity behavior of supported palladium nanoparticles","volume":"9","author":"Nadgeri","year":"2008","journal-title":"Catal. Commun."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1761","DOI":"10.1021\/cr400357r","article-title":"Catalytic reactions of acetylene: A feedstock for the chemical industry revisited","volume":"114","author":"Trotus","year":"2014","journal-title":"Chem. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"501","DOI":"10.1016\/j.cej.2011.06.029","article-title":"Study on deactivation of Ni\/Al2O3 catalyst for liquid phase hydrogenation of crude 1,4-butanediol aqueous solution","volume":"181\u2013182","author":"Li","year":"2012","journal-title":"Chem. Eng. J."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"439","DOI":"10.1016\/j.cattod.2004.06.054","article-title":"Hydrogenation of 2-butyne-1,4-diol in supercritical carbon dioxide promoted by stainless steel reactor wall","volume":"93\u201395","author":"Zhao","year":"2004","journal-title":"Catal. Today"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"233","DOI":"10.1016\/j.apcata.2013.06.020","article-title":"Heterogeneous CaO-ZrO2 acid-base bifunctional catalysts for vapor-phase selective dehydration of 1,4-butanediol to 3-buten-1-ol","volume":"466","author":"Zhang","year":"2013","journal-title":"Appl. Catal. A Gen."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Li, H.T., Ban, L.J., Wang, Z.P., Meng, P.F., Zhang, Y., Wu, R.F., and Zhao, Y.X. (2019). Regulation of Cu species in CuO\/SiO2 and its structural evolution in ethynylation reaction. Nanomaterials, 9.","DOI":"10.3390\/nano9060842"},{"key":"ref_8","first-page":"540","article-title":"Effect of NaOH concentration on structure and catalytic performance of Cu2O for formaldehyde ethynylation","volume":"30","author":"Yang","year":"2016","journal-title":"J. Mol. Catal."},{"key":"ref_9","unstructured":"Eugene, V.H., and Pispacaway, N.J. (1975). Ethynylation Catalyst and Process for Production Alkynols by Low Pressure Reactions. (US 3920759)."},{"key":"ref_10","unstructured":"Zak, D.J. (1978). Butynediol Production. (US 4085151)."},{"key":"ref_11","unstructured":"Fremont, J.M. (1978). Preparation of Butynediol Using Bismuth Modified Spheroidal Malachite. (4127,734), U.S. Patent."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1016\/j.apcata.2004.08.027","article-title":"New diol process: 1,3-propanediol and 1,4-butanediol","volume":"280","author":"Haas","year":"2005","journal-title":"Appl. Catal. A Gen."},{"key":"ref_13","first-page":"344","article-title":"Preparation of core-shell CuO-Bi2O3@meso-SiO2 catalyst and its catalytic performance for formaldehyde ethynylation","volume":"23","author":"Ma","year":"2015","journal-title":"Ind. Catal. (China)"},{"key":"ref_14","first-page":"363","article-title":"Researches on activation process of CuO-Bi2O3 \/SiO2-MgO catalyst in formaldehyde ethynylation reaction","volume":"22","author":"Luo","year":"2014","journal-title":"Ind. Catal. (China)"},{"key":"ref_15","first-page":"233","article-title":"Preparation of CuO-Bi2O3\/SiO2-MgO catalyst and its ethynylation performance","volume":"26","author":"Zheng","year":"2012","journal-title":"J. Mol. Catal. (China)"},{"key":"ref_16","first-page":"2098","article-title":"Preparation of magnetic CuO-Bi2O3\/Fe3O4-SiO2-MgO catalyst and its catalytic performance for formaldehyde ethynylation","volume":"66","author":"Wang","year":"2015","journal-title":"J. Chem. Ind. Eng."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Wang, Z.P., Niu, Z.Z., Hao, Q.A., Ban, L.J., Li, H.T., Zhao, Y.X., and Jiang, Z. (2019). Enhancing the ethynylation performance of CuO-Bi2O3 nanocatalysts by tuning Cu-Bi interactions and phase structures. Catalysts, 9.","DOI":"10.3390\/catal9010035"},{"key":"ref_18","first-page":"2512","article-title":"Support effect of Cu2O\/TiO2 employed in formaldehyde ethynylation","volume":"69","author":"Li","year":"2018","journal-title":"J. Chem. Ind. Eng."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Wang, Z.P., Ban, L.J., Meng, P.F., Li, H.T., and Zhao, Y.X. (2019). Ethynylation of Formaldehyde over Binary Cu-Based Catalysts: Study on Synergistic Effect between Cu+ Species and Acid\/Base Sites. Nanomaterials, 9.","DOI":"10.3390\/nano9071038"},{"key":"ref_20","first-page":"124","article-title":"Study on catalytic of CuO-ZnO catalyst prepared by different precipitants","volume":"33","author":"Li","year":"2019","journal-title":"Ind. Catal. (China)"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"5091","DOI":"10.1007\/s11164-017-3050-0","article-title":"Facile synthesis of Fe2O3\/Cu2O nanocomposite and its visible light photocatalytic activity for the degradation of cationic dyes","volume":"43","author":"Lakhera","year":"2017","journal-title":"Res. Chem. Intermed."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"70","DOI":"10.1021\/sc400313y","article-title":"Nanostructured ternary nanocomposite of rGO\/CNTs\/MnO2 for high-rate supercapacitors","volume":"2","author":"Jiang","year":"2014","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"883","DOI":"10.1039\/C3CE41766B","article-title":"Hierarchical Au-CuO nanocomposite from redox transformation reaction for surface enhanced Raman scattering and clock reaction","volume":"16","author":"Pal","year":"2014","journal-title":"CrystEngComm"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"5538","DOI":"10.1039\/c0jm00638f","article-title":"Magnetite\/Graphene composites: Microwave irradiation synthesis and enhanced cycling and rate performances for lithium ion batteries","volume":"20","author":"Wang","year":"2010","journal-title":"J. Mater. Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"9052","DOI":"10.1039\/c2jm00153e","article-title":"One-pot synthesis of tunable Fe3O4\u2013MnO2 core\u2013shell nanoplates and their applications for water purification","volume":"22","author":"Zhao","year":"2012","journal-title":"J. Mater. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"6670","DOI":"10.1021\/la202569q","article-title":"Galvanically replaced hollow Au\u2013Ag nanospheres: Study of their surface plasmon resonance","volume":"28","author":"Choi","year":"2012","journal-title":"Langmuir"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"9173","DOI":"10.1021\/am502866t","article-title":"Account of nitroarene reduction with size- and facet-controlled CuO\u2013MnO2 nanocomposites","volume":"6","author":"Pal","year":"2014","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"7606","DOI":"10.1021\/acs.langmuir.7b01540","article-title":"Decorating of Ag and CuO on Cu nanoparticles for enhanced high catalytic activity to the degradation of organic pollutants","volume":"33","author":"Liang","year":"2017","journal-title":"Langmuir"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"388","DOI":"10.1016\/j.ultsonch.2015.10.018","article-title":"Sonochemical synthesis of Cu2O nanocubes for enhanced chemiluminescence applications","volume":"29","author":"Kaviyarasan","year":"2016","journal-title":"Ultrason. Sonochem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"58","DOI":"10.1016\/j.cattod.2017.03.020","article-title":"Interparticle double charge transfer mechanism of heterojunction \u03b1-Fe2O3\/Cu2O mixed oxide catalysts and its visible light photocatalytic activity","volume":"300","author":"Lakheraa","year":"2018","journal-title":"Catal. Today"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"213","DOI":"10.1007\/BF01379349","article-title":"The long wave modes of the Cu2O Lattice","volume":"171","author":"Huang","year":"1963","journal-title":"Zeitschrift f\u00fcr Physik"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2201","DOI":"10.1016\/S0022-3697(73)80067-8","article-title":"The dielectric and lattice vibrational spectrum of cuprous oxide","volume":"34","author":"Dawson","year":"1973","journal-title":"J. Phys. Chem. Solids"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"2640","DOI":"10.1002\/ejic.201201382","article-title":"Copper(I) oxide nanocrystals-one step synthesis, characterization, formation mechanism and photocatalytic properties","volume":"14","author":"Singhal","year":"2013","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"9545","DOI":"10.1039\/C5NR01277E","article-title":"Surface- and tip-enhanced Raman spectroscopy reveals spin-waves in iron oxide nanoparticles","volume":"7","author":"Rodriguez","year":"2015","journal-title":"Nanoscale"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"4301","DOI":"10.1023\/A:1004884302755","article-title":"A micro-Raman study of iron-titanium oxides obtained by sol-gel synthesis","volume":"35","author":"Bersani","year":"2000","journal-title":"J. Mater. Sci."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1261","DOI":"10.1021\/ja209662v","article-title":"Synthesis of Cu2O nanocrystals from cubic to rhombic dodecahedral structures and their comparative photocatalytic activity","volume":"134","author":"Huang","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"470","DOI":"10.1016\/j.jcis.2018.04.106","article-title":"Construction of p-n heterojunction film of Cu2O\/a-Fe2O3 for efficiently photoelectrocatalytic degradation of oxytetracycline","volume":"526","author":"Cheng","year":"2018","journal-title":"J. Colloid Interface Sci."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"603","DOI":"10.1007\/s11705-017-1661-z","article-title":"Effects of preparation methods on the activity of CuO\/CeO2 catalysts for CO oxidation","volume":"11","author":"Shang","year":"2017","journal-title":"Front. Chem. Sci. Eng."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"8631","DOI":"10.1021\/acsami.5b00822","article-title":"Enhanced photoreduction CO2 activity over direct z-scheme \u03b1-Fe2O3\/Cu2O heterostructures under visible light lrradiation","volume":"7","author":"Wang","year":"2015","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"6","DOI":"10.1016\/j.apsusc.2014.02.006","article-title":"XPS analysis of oleylamine\/oleic acid capped Fe3O4 nanoparticles as a function of temperature","volume":"303","author":"Wilson","year":"2014","journal-title":"Appl. Surf. Sci."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"18355","DOI":"10.1021\/jp8060027","article-title":"Facile synthesis of Cu2O nanocrystals with systematic shape evolution from cubic to octahedral structures","volume":"112","author":"Kuo","year":"2008","journal-title":"J. Phys. Chem. C"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"14159","DOI":"10.1021\/jp903928p","article-title":"Synthesis of submicrometer-sized Cu2O crystals with morphological evolution from cubic to hexapod structures and their comparative photocatalytic activity","volume":"113","author":"Ho","year":"2009","journal-title":"J. Phys. Chem. C"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"4219","DOI":"10.1002\/ejic.200900730","article-title":"Cu2O nanocube-catalyzed cross-coupling of aryl halides with phenols via ullmann coupling","volume":"28","author":"Kim","year":"2009","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"3730","DOI":"10.1016\/j.tet.2010.03.065","article-title":"PEG3400-Cu2O-Cs2CO3: An efficient and recyclable microwave-enhanced catalytic system for ligand-free ullmann arylation of indole and benzimidazol","volume":"66","author":"Colacino","year":"2010","journal-title":"Tetrahedron"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"163","DOI":"10.1016\/j.cattod.2011.06.002","article-title":"Structure and reactivity of Au-Rh bimetallic clusters on titanate nanowires, nanotubes and TiO2(110)","volume":"181","author":"Kiss","year":"2012","journal-title":"Catal. Today"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"2167","DOI":"10.1021\/la902674u","article-title":"Formation of Rh-Au Core-Shell Nanoparticles on TiO2(110) Surface Studied by STM and LEIS","volume":"26","author":"Majzik","year":"2010","journal-title":"Langmuir"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"919","DOI":"10.1039\/C2TA00591C","article-title":"A new strategy for the surface-free-energy-distribution induced selective growth and controlled formation of Cu2O-Au hierarchical heterostructures with a series of morphological evolutions","volume":"1","author":"Zhu","year":"2013","journal-title":"J. Mater. Chem. A"}],"container-title":["Nanomaterials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-4991\/9\/9\/1301\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T13:18:56Z","timestamp":1760188736000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-4991\/9\/9\/1301"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,9,11]]},"references-count":47,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2019,9]]}},"alternative-id":["nano9091301"],"URL":"https:\/\/doi.org\/10.3390\/nano9091301","relation":{},"ISSN":["2079-4991"],"issn-type":[{"value":"2079-4991","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,9,11]]}}}