Металлорганические каркасные структуры и композиты на их основе: особенности строения, методы синтеза, электрохимические свойства и перспективы (обзор)

Представлен обзор различных видов металлорганических каркасов (МОК) и особенностей их структуры, представлена классификация. Рассмотрены основные методы и подходы к синтезу как самих МОК, так и композиционных материалов на их основе.

Структура МОК представляет собой регулярную трехмерную решетку, образованную органическими линкерами и металлическими кластерами. На примере анализа литературных данных по синтезу МОК и изучению их структуры показано, что характер взаимосвязей и типы металлов могут существенным образом влиять на пространственное построение и размер кристаллов МОК: они могут быть нано-, микро- и мезоразмерными, плотными и пористыми, объемными и слоистыми. Это все определяет их широкий спектр свойств и возможности применения.

Рассмотрены перспективы и способы управления и контроля формы кристаллов, их размера и пространственным взаимосвязям между органическими компонентами и ионами металлов.

Основное внимание уделено цеолитоподобным каркасам (ZIF) как наиболее интересным с точки зрения строения, синтеза и применения в качестве материалов для электрохимических источников тока. Рассмотрены возможности модификации и контроля свойств этих МОК и композиционных материалов на их основе за счет управления составом, создания пористых структур и внедрения в них примесей, в том числе и с магнитными свойствами. Представлены различные варианты синтеза сложных композиционных материалов путем контролируемого пиролиза МОК как простого и масштабируемого процесса. Продемонстрировано влияние условий термообработки на конечные свойства, а также перспективы использования таких материалов в приложении электрохимии.

В качестве одного из вариантов изменения свойств МОК и композиционных материалов на их основе представлен подход, основанный на легировании МОК со структурой ZIF-67 другим металлом. В частности, научным коллективом авторов реализован синтез кобальтовых МОК, в которых кобальт частично замещен марганцем на стадии синтеза. Помимо этого, использована простая методика синтеза путем соосаждения в водном растворе, модифицированная ультразвуковым воздействием, которое сокращает продолжительность синтеза. Электрохимические исследования показали, что удельная электрохимическая емкость электродов из пиролизованных МОК с частичным замещением кобальта на марганец значительно выше, чем у материалов без марганца. С увеличением содержания марганца в МОК возрастает как удельная емкость, так и плотность энергии. Легирование МОК марганцем позволяет значительно (от 100 до 298 Ф/г при плотности тока 0,25 А/г) улучшить электрохимические характеристики материалов электродов для гибридных суперконденсаторов на их основе. Полученные авторами результаты свидетельствуют о том, что замещение кобальта марганцем является эффективным способом повышения электрохимических характеристик МОК.

Продемонстрировано, что разработка новых подходов к дизайну композитных материалов на основе МОК, а также исследование физико-химических закономерностей взаимодействия этих материалов с различного рода носителями является актуальной задачей.

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