CONTENTS / СОДЕРЖАНИЕ Dmitry V. Kazachkin, David R. Luebke, Vladimir I. Kovalchuk, and Julie L. d’Itri Hydrogen-Assisted 1,2-Dichloroethane Dechlorination Catalyzed by Pt-Cu/SiO2 Active Sites : Insights into the Nature of Ethylene-Selective – 303 – Alexey N. Lukianov, Olga N. Kononova and Sergey V. Kachin Calculation of Protolytic Equilibria Parameters on a Surface of Some Carbon Adsorbents According to Potentiometric Titration Data – 326 – Tatiana G. Shendrik, Valentina V. Siminova, Nikolai V. Chesnokov and Boris N. Kuznetsov Properties of Active Carbons Produced by Thermochemical Transformation of Lignin, Brown Coal and Oil Slime Mixtures – 336 – Anatoly I. Rubailo and Andrey V. Oberenko Polycyclic Aromatic Hydrocarbons as Priority Pollutants – 344 – Irina G. Sudakova, Boris N. Kuznetsov, Natalia V. Garyntseva, Nina I. Pavlenko and Natalia M. Ivanchenko Functional and Thermal Analysis of Suberin Isolated from Birch Bark – 355 – 2008 1 (4) Editorial board for Chemistry: Nikolai V. Chesnokov Lubov ’ K. Altunina Natalia G. Bazarnova Vasiliy A. Babkin Vicente Cebolla Viktor M. Denisov Zinfer R. Ismagilov Sergey V. Kachin Sergey D. Kirik Wolfgang Klose Vladimir I. Kovalchuk Vladimir A. Likholobov Yuri L. Mikhlin Gennady L. Pashkov Anatoly I. Rubailo Tatyana V. Ryazanova Vladimir A. Sobyanin Valeri E. Tarabanko Tatyana G. Shendrik Maxim L. Shchipko Jean V. Weber Valeri E. Tarabanko, Olga A. Ulyanova, Galina S. Kalachova, Valentina V. Chuprova and Nikolai V. Tarabanko Study of Plant Growth Promoting Activity and Chemical Composition of Pine Bark after Various Storage Periods – 363 – Владимир А. <...> Кузнецов Влияние модифицирующих добавок на карбонизацию смесей березовых опилок с каменноугольным пеком Свидетельство о регистрации СМИ ПИ № ФС77-28-726 от 29.06.2007 г. – 389 – Светлана А. <...> Chemistry 4 (2008 1) 303-325 ~ ~ ~ УДК 546 Hydrogen-Assisted 1,2-Dichloroethane Dechlorination Catalyzed by Pt-Cu/SiO2 : Insights into the Nature of Ethylene-Selective Active Sites Dmitry V. Kazachkin, David R. Luebke, Vladimir I. Kovalchuk* and Julie L. d’Itri Department of Chemical Engineering, University of Pittsburgh <...>
Журнал_Сибирского_федерального_университета._Сер._Химия_№4_2008.pdf
Журнал Сибирского федерального университета
Journal of Siberian Federal University
Химия
Chemistry
Редакционный совет
академик РАН Е.А.Ваганов
академик РАН К.С.Александров
академик РАН И.И.Гительзон
академик РАН В.Ф.Шабанов
чл.-к. РАН, д-р физ.-мат.наук
А.Г.Дегерменджи
чл.-к. РАН, д-р физ.-мат. наук
В.Л.Миронов
чл.-к. РАН, д-р техн. наук
Г.Л.Пашков
чл.-к. РАН, д-р физ.-мат. наук
В.В.Шайдуров
чл.-к. РАО, д-р физ.-мат. наук
В.С. Соколов
Editorial Advisory Board
Chairman:
Eugene A. Vaganov
Members:
Kirill S. Alexandrov
Josef J. Gitelzon
Vasily F. Shabanov
Andrey G. Degermendzhy
Valery L. Mironov
Gennady L. Pashkov
Vladimir V. Shaidurov
Veniamin S. Sokolov
Editorial Board:
Editor-in-Chief:
Mikhail I. Gladyshev
Founding Editor:
Vladimir I. Kolmakov
Managing Editor:
Olga F. Alexandrova
Executive Editor for Chemistry:
Boris N. Kuznetsov
Редактор И.А. Вейсиг Корректор Т.Е. Бастрыгина
Компьютерная верстка И.В. Гревцовой, Е.В. Гревцовой
Подписано в печать 22.12.2008 г. Формат 19х27. Усл. печ. л. 6,6.
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Отпечатано в ИПК СФУ. 660041 Красноярск, пр. Свободный, 79.
CONTENTS / СОДЕРЖАНИЕ
Dmitry V. Kazachkin, David R. Luebke,
Vladimir I. Kovalchuk, and Julie L. d’Itri
Hydrogen-Assisted 1,2-Dichloroethane Dechlorination Catalyzed
by Pt-Cu/SiO2
Active Sites
: Insights into the Nature of Ethylene-Selective
– 303 –
Alexey N. Lukianov, Olga N. Kononova
and Sergey V. Kachin
Calculation of Protolytic Equilibria Parameters on a Surface of
Some Carbon Adsorbents According to Potentiometric Titration
Data
– 326 –
Tatiana G. Shendrik, Valentina V. Siminova,
Nikolai V. Chesnokov and Boris N. Kuznetsov
Properties of Active Carbons Produced by Thermochemical
Transformation of Lignin, Brown Coal and Oil Slime Mixtures
– 336 –
Anatoly I. Rubailo and Andrey V. Oberenko
Polycyclic Aromatic Hydrocarbons as Priority Pollutants
– 344 –
Irina G. Sudakova, Boris N. Kuznetsov,
Natalia V. Garyntseva, Nina I. Pavlenko
and Natalia M. Ivanchenko
Functional and Thermal Analysis of Suberin Isolated from Birch
Bark
– 355 –
2008 1 (4)
Стр.1
Editorial board for Chemistry:
Nikolai V. Chesnokov
Lubov ’ K. Altunina
Natalia G. Bazarnova
Vasiliy A. Babkin
Vicente Cebolla
Viktor M. Denisov
Zinfer R. Ismagilov
Sergey V. Kachin
Sergey D. Kirik
Wolfgang Klose
Vladimir I. Kovalchuk
Vladimir A. Likholobov
Yuri L. Mikhlin
Gennady L. Pashkov
Anatoly I. Rubailo
Tatyana V. Ryazanova
Vladimir A. Sobyanin
Valeri E. Tarabanko
Tatyana G. Shendrik
Maxim L. Shchipko
Jean V. Weber
Valeri E. Tarabanko, Olga A. Ulyanova,
Galina S. Kalachova, Valentina V. Chuprova
and Nikolai V. Tarabanko
Study of Plant Growth Promoting Activity and Chemical Composition
of Pine Bark after Various Storage Periods
– 363 –
Владимир А. Левданский, Александр В. Левданский,
Борис Н. Кузнецов
Влияние ортофосфорной кислоты на химические превращения
бетулинола в бутаноле, изобутаноле и уксусной кислоте
– 369 –
Светлана А. Козлова, Владимир А. Парфенов,
Людмила С. Тарасова, Сергей Д. Кирик
Состояние силанольного покрытия мезоструктурированного
силикатного материала МСМ-41 в результате постсинтетической
активации
– 376 –
Светлана И. Цыганова, Александр Н. Швецов,
Ирина В. Королькова, Николай В. Чесноков,
Борис Н. Кузнецов
Влияние модифицирующих добавок на карбонизацию смесей
березовых опилок с каменноугольным пеком
Свидетельство о регистрации СМИ
ПИ № ФС77-28-726 от 29.06.2007 г.
– 389 –
Светлана А. Быстрякова, Людмила П. Рубчевская
Состав фосфолипидов хвои сосны сибирской
– 399 –
Правила представления статей для публикации
– 405 –
Стр.2
Journal of Siberian Federal University. Chemistry 4 (2008 1) 303-325
~ ~ ~
УДК 546
Hydrogen-Assisted 1,2-Dichloroethane Dechlorination Catalyzed
by Pt-Cu/SiO2
: Insights into the Nature
of Ethylene-Selective Active Sites
Dmitry V. Kazachkin, David R. Luebke,
Vladimir I. Kovalchuk* and Julie L. d’Itri
Department of Chemical Engineering, University of Pittsburgh,
Pittsburgh, Pennsylvania 15261 1
Received 24.11.2008, received in revised form 15.12.2008, accepted 22.12.2008
Differently pretreated silica-supported Pt, Cu, and Pt-Cu catalysts with Cu to Pt atomic ratio of 1 to 6
have been investigated by a combination of reaction kinetics and FTIR spectroscopic studies in order
to understand the factors that control the selectivity toward ethylene and ethane in the CH2
ClCH2
Cl+H2
reaction. Carbon monoxide adsorption was used to probe the electronic modification of Pt and Cu as
well as the nature of ethylene-selective active sites. It was shown that there is a very limited, if any,
electronic interaction between Pt and Cu in the bimetallic catalysts reduced at 493 K. However, the
Pt-Cu catalysts, for which no dipole-dipole coupling shift was observed in the IR spectra of adsorbed
CO suggesting extremely small Pt ensembles on the catalyst surface, demonstrated high ethylene
selectivity in the 1,2-dichloroethane dechlorination. Electronic interactions between Pt and Cu have
been discovered for the Pt-Cu/SiO2
by a higher stability of Cu0
in the FTIR spectra of adsorbed CO. The initial ethylene selectivity of the catalysts was
inversely proportional to the dipole-dipole coupling shift. The observations are consistent with the
idea that the nature of the Pt-Cu species, viz., alloy particles as opposed to Cu/Pt overlayers, does
not control the reaction selectivity, which is a function of the Pt ensemble size on the surface of Pt-Cu
moieties.
Keywords: hydrogen-assisted dechlorination, 1,2-dichlorothane, ethylene, Pt-Cu catalysts, infrared
spectroscopy, singleton frequency, dipole-dipole coupling.
Introduction
It has been discovered a decade ago
that a combination of Pt or Pd with another
metal deposited on a solid support catalyzes
hydrodechlorination of vicinal dichloroalkanes
such as 1,2-dichloroethane and 1,2©
Siberian Federal University. All rights reserved
dichloropropane toward the formation of the
corresponding alkene, viz., ethylene or propylene
[1-3]. Such a chemistry looks surprising because
any catalyst that activates H2
catalysts reduced at 773 K. The interactions manifested themselves
-CO adsorption complexes in vacuum and by an increase in intensity of the
Pt-CO band in the FTIR spectra upon evacuation of CO from the gas phase suggesting the formation
of Pt-Cu solid solutions. The higher temperature reduction resulted in the dipole-dipole coupling shift
of 6 to 19 cm-1
should also
hydrogenate the product olefin. As chloroalkanes
are common environmental pollutants and alkenes
* Corresponding author E-mail address: vkovalchuk@mckasd.net
1
– 303 –
Стр.3