alternativeАльтернативная энергетика и экология (ISJAEE)Alternative Energy and Ecology (ISJAEE)1608-8298Международный издательский дом научной периодики "Спейс10.15518/isjaee.2017.28-30.038-053alternative-1236Research ArticleВОДОРОДНАЯ ЭКОНОМИКАHYDROGEN ECONOMYИЗОТОПНЫЙ ОБМЕН МЕЖДУ ВОДОРОДОМ ГАЗОВОЙ ФАЗЫ И ПРОТОНПРОВОДЯЩИМИ ОКСИДАМИ: ТЕОРИЯ И ЭКСПЕРИМЕНТISOTOPIC EXCHANGE BETWEEN HYDROGEN FROM THE GAS PHASE AND PROTON-CONDUCTING OXIDES: THEORY AND EXPERIMENTАнаньевМ. В.AnanyevM. V.

д-р хим. наук, зав. лабораторией ТОТЭ, директор ИВТЭ УрО РАН

D.Sc. in Chemistry, the Head of laboratory of SOFC, Director of Institute of High Temperature Electrochemistry of the Ural Branch of the RAS

m.ananyev@mail.ruФарленковА. С.FarlenkovA. S.

инженер/аспирант, Институт высокотемпературной электрохимии УрО РАН

engineer / Ph.D. student, Institute of High-Temperature Electrochemistry, UB RAS

m.ananyev@mail.ruКурумчинЭ. Х.KurumchinE. Kh.

д-р хим. наук, главный научный сотрудник ИВТЭ УрО РАН

D.Sc. in Chemistry, Chief Research Scientist

m.ananyev@mail.ruИнститут высокотемпературной электрохимии УрО РАН; Уральский федеральный университет имени первого президента России Б.Н. ЕльцинаРоссияInstitute of High Temperature Electrochemistry of the Ural Branch of the RAS; Ural Federal University named after the first President of Russia B.N. YeltsinRussian FederationИнститут высокотемпературной электрохимии УрО РАНРоссияInstitute of High Temperature Electrochemistry of the Ural Branch of the RASRussian Federation201711012018028-303853Copyright © Международный издательский дом научной периодики "Спейс, 20182018Международный издательский дом научной периодики "СпейсМеждународный издательский дом научной периодики "Спейсhttps://www.isjaee.com/jour/about/submissions#copyrightNoticehttps://www.isjaee.com/jour/article/view/1236

Процесс взаимодействия изотопов водорода газовой фазы с протонпроводящими оксидами со структурой перовскита La1−xSrxScO3−α (x = 0; 0,04) изучали методом изотопного обмена водорода с уравновешиванием изотопного состава газовой фазы в интервалах температуры T = 300÷ 800 ºC и давления водорода pH2 ÷ 2 20 мбар. Разработана новая кинетическая модель для обработки экспериментальных данных по изотопному обмену водорода с учетом изотопных эффектов, которую успешно применили для обработки результатов проведенных экспериментов. Рассчитаны скорости межфазного обмена изотопов водорода с оксидами La1−xSrxScO3−α (x = 0; 0,04). По равновесным значениям доли метки в газовой фазе определены мольные доли изотопов водорода в исследуемых соединениях. Установлено, что растворимость дейтерия выше, чем протия, тогда как коэффициент обмена дейтерия с поверхностью протонпроводящего оксида La0,96Sr0,04ScO3−α меньше, чем коэффициент обмена протия. Наблюдаемый таким образом термодинамический изотопный эффект может быть связан с отличием в энергиях нулевых колебаний OH- и OD-дефектов и молекулярных H2 и D2, при этом кинетический изотопный эффект можно объяснить отличием в прочности связей OH и OD. Показано, что лимитирующей стадией обмена водорода является процесс обмена между формами водорода в газовой фазе и в адсорбционном слое протонпроводящего оксида (стадия диссоциативной адсорбции водорода). Впервые предложен новый статистический критерий, который позволил выделить неоднородности поверхности оксида, вызванные не только его естественной шероховатостью, но и наличием различных изотопов водорода (протия и дейтерия) с различными энергиями связи на поверхности. Активность исследованных протонпроводящих оксидов по отношению к обмену с водородом газовой фазы оказалась на уровне, сопоставимом со значениями скорости межфазного обмена водорода для оксидов на основе цератов и цирконатов щёлочноземельных металлов. Высокая каталитическая активность по отношению к процессу обмена с водородом газовой фазы в восстановительных атмосферах позволяет рассматривать протонпроводящие оксиды на основе скандата лантана как весьма перспективные электролиты для различных электрохимических приложений.

 

 

 

 

The interaction of gaseous hydrogen isotopes from the gas phase with proton-conducting oxides with the perovskite structure La1−xSrxScO3−α (x = 0; 0.04) was studied by means of the hydrogen isotope exchange with gas phase equilibration in the temperature range T = 300−800 ºC and in hydrogen pressure range pH2 = 2−20 mbar. A novel kinetic model for the hydrogen isotope exchange experimental data treatment taking into account the isotopic effects was developed. This model was implemented for the obtained experimental results. The heterogeneous exchange rates of hydrogen isotopes with investigated oxides La1−xSrxScO3−α (x = 0; 0.04) were calculated. The mole fractions of hydrogen isotopes were determined for the investigated materials. It was found that deuterium uptake is higher in comparison with protium, whereas the deuterium surface exchange coefficient for the proton-conducting oxide La0.96Sr0.04ScO3–α is smaller in comparison with the protium surface exchange coefficient. The thermodynamic isotope effect can be caused by the difference of energy of zero-point oscillations between OH- and OD-defects and molecular H2 and D2. The kinetic isotope effect can be explained by the different strength of OH and OD bonds. The rate determining stage of hydrogen exchange is shown to be the process of exchange between the forms of hydrogen in the gas phase and in the adsorption layer of the proton-conducting oxide (the stage of dissociative hydrogen adsorption). For the first time, a new statistical criterion is proposed that allows dividing the observed surface inhomogeneities caused by not only the natural surface roughness but also the presence of different isotopes of hydrogen (protium and deuterium) with different binding energies on a solid surface. The activity of the investigated proton-conducting oxides with respect to the hydrogen heterogeneous exchange is comparable to the heterogeneous hydrogen exchange activity for oxides based on cerates and zirconates of alkaline earth metals. High catalytic activity with respect to the process of hydrogen exchange from the gas phase in reducing atmospheres allows us to consider the proton-conducting oxides based on the lanthanum scandates as the very promising electrolytes for numerous electrochemical applications.

 

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The authors declare that there are no conflicts of interest present.