{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,27]],"date-time":"2026-03-27T05:06:18Z","timestamp":1774587978691,"version":"3.50.1"},"reference-count":49,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2004,3,16]],"date-time":"2004-03-16T00:00:00Z","timestamp":1079395200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2004,4,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The catalytic destruction of carbon tetrachloride in the presence of steam, CCl<jats:sub>4<\/jats:sub> + 2\u2009H<jats:sub>2<\/jats:sub>O\u21924\u2009HCl + CO<jats:sub>2<\/jats:sub>, was investigated at 200\u2013350\u2009\u00b0C over a series of lanthanide (La, Ce, Pr and Nd) and alkaline\u2010earth metal (Mg, Ca, Sr and Ba) oxide\u2010based catalysts with kinetic experiments, Raman spectroscopy, X\u2010ray photoelectron spectroscopy, IR spectroscopy, X\u2010ray diffraction, and DFT calculations. This new catalytic reaction was achieved by combining destructive adsorption of CCl<jats:sub>4<\/jats:sub> on a basic oxide surface and concurrent dechlorination of the resulting partially chlorinated solid by steam. The combination of the two noncatalytic reactions into a catalytic cycle provided a rare opportunity in heterogeneous catalysis for studying the nature and extent of surface participation in the overall reaction chemistry. The reaction is proposed to proceed over a terminal lattice oxygen site with stepwise donation of chlorine atoms from the hydrocarbon to the surface and formation of the gas\u2010phase intermediate COCl<jats:sub>2<\/jats:sub>, which is readily readsorbed at the catalyst surface to form CO<jats:sub>2<\/jats:sub>. In a second step, the active catalyst surface is regenerated by steam with formation of gas\u2010phase HCl. Depending on the reaction conditions, the catalytic material was found to transform dynamically from the metal oxide state to the metal oxide chloride or metal chloride state due to the bulk diffusion of oxygen and chlorine atoms. A catalyst obtained from a 10 wt\u2009% La<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>\/Al<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> precursor exhibited the highest destruction rate: 0.289 g CCl<jats:sub>4<\/jats:sub> h<jats:sup>\u22121<\/jats:sup>\u2009g<jats:sup>\u22121<\/jats:sup> catalyst at 350\u2009\u00b0C, which is higher than that of any other reported catalyst system.<\/jats:p>","DOI":"10.1002\/chem.200305442","type":"journal-article","created":{"date-parts":[[2004,3,25]],"date-time":"2004-03-25T13:59:58Z","timestamp":1080223198000},"page":"1637-1646","source":"Crossref","is-referenced-by-count":38,"title":["Low\u2010Temperature Destruction of Carbon Tetrachloride over Lanthanide Oxide\u2010Based Catalysts: From Destructive Adsorption to a Catalytic Reaction Cycle"],"prefix":"10.1002","volume":"10","author":[{"given":"Pieter","family":"Van der Avert","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Simon G.","family":"Podkolzin","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Olga","family":"Manoilova","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hendrik","family":"de Winne","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Bert M.","family":"Weckhuysen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2004,3,24]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527613380"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1080\/00102208308923710"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1080\/00102208408923729"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0926-3373(00)00231-9"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/jctb.5020250402"},{"key":"e_1_2_6_3_4","doi-asserted-by":"publisher","DOI":"10.1016\/S0920-5861(99)00169-8"},{"key":"e_1_2_6_3_5","doi-asserted-by":"publisher","DOI":"10.1016\/S0926-860X(00)00577-9"},{"key":"e_1_2_6_3_6","doi-asserted-by":"publisher","DOI":"10.1006\/jcat.2000.2895"},{"key":"e_1_2_6_3_7","doi-asserted-by":"publisher","DOI":"10.1016\/S0926-3373(99)00030-2"},{"key":"e_1_2_6_4_2","first-page":"316","volume":"6","author":"Wilde M.","year":"1994","journal-title":"Chem. Tech."},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp980185k"},{"key":"e_1_2_6_6_2","first-page":"1993","author":"Koper O.","journal-title":"Chem. Mater."},{"key":"e_1_2_6_6_3","first-page":"500","journal-title":"5"},{"key":"e_1_2_6_6_4","doi-asserted-by":"publisher","DOI":"10.1021\/la00006a035"},{"key":"e_1_2_6_6_5","first-page":"1997","author":"Koper O.","journal-title":"Chem. Mater."},{"key":"e_1_2_6_6_6","first-page":"2481","journal-title":"9"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/es00056a010"},{"key":"e_1_2_6_8_2","unstructured":"B. M. Weckhuysen G. Mestl M. P. Rosynek J. H. Lunsford ACS Division of Environmental Chemistry Preprints of Extended Abstracts1998 38 31;"},{"key":"e_1_2_6_8_3","unstructured":"Chem.Eng.News April 201998 71."},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp980185k"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/a901847f"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200290029"},{"key":"e_1_2_6_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200290030"},{"key":"e_1_2_6_11_4","unstructured":"Chem.Eng.News January 6 2003 24."},{"key":"e_1_2_6_12_2","unstructured":"B.Weckhuysen R.Schoonheydt P.Van der Avert WO 03057318A1."},{"key":"e_1_2_6_13_2","unstructured":"Several attempts to perform similar experiments with pure CeO2and CeCl3at 300\u2009\u00b0C failed. This can be attributed to the redox change (Ce3+\/Ce4+) associated with the destructive adsorption of CCl4over CeO2and the steam dechlorination of CeCl3. Indeed previous Raman spectroscopic experiments showed that CeO2is transformed to CeCl3 but higher reaction temperatures are required than with La2O3.[10]This requirement for higher temperature was specific to pure Ce oxide samples and did not apply to those supported on alumina."},{"key":"e_1_2_6_14_2","unstructured":"To test this hypothesis we also synthesized a series of La2O3materials with surface areas between 20 and 55 m2\u2009g\u22121. The surface areas of these materials however decrease during catalysis to values between 10 and 30 m2\u2009g\u22121. A small effect of the surface area was noticeable although a support material appeared to be essential for maintaining high degrees of lanthanide oxide dispersion."},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0920-5861(99)00134-0"},{"key":"e_1_2_6_16_2","unstructured":"Similar observations were also made for the catalytic destruction of other CHCs such as CH2Cl2and CHCl3."},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/a909552g"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0039969"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/0584-8539(79)80204-4"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0925-8388(96)02632-1"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1016\/0584-8539(81)80055-4"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0277-5387(97)00065-X"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1366\/0003702001949924"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1366\/0003702001950175"},{"key":"e_1_2_6_25_2","unstructured":"Although we have prepared and tested several series of La2O3and LaOCl materials differing in their surface areas it is very difficult to compare the relative activity of the individual phases since the materials readily transform from one phase into another due to the surface chlorination\/dechlorination reactions and bulk O\/Cl diffusion. However our experiments show conclusively that the LaCl3phase is inactive for CCl4decomposition."},{"key":"e_1_2_6_26_2","unstructured":"Although several attempts to record Raman spectra for the 10 wt\u2009% La2O3\/Al2O3catalyst under reaction conditions were unsuccessful in some rare cases we were able to resolve weak Raman bands at 337 and 437 cm\u22121on top of a fluorescence background. These Raman band indicate the formation of LaOCl on the support."},{"key":"e_1_2_6_27_2","volume-title":"Infrared and Raman Spectra of Inorganic and Coordination Compounds Part A: Theory and Applications in Inorganic Chemistry","author":"Nakamoto K.","year":"1997"},{"key":"e_1_2_6_28_2","volume-title":"Handbook of X\u2010ray photoelectron Spectroscopy","author":"Wagner C. D.","year":"1979"},{"key":"e_1_2_6_29_2","first-page":"1488","volume":"25","author":"Buznik V. M.","year":"1980","journal-title":"Zh. Neorg. 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