Low‐Dimensional Metal‐Organic Frameworks and their Diverse Functional Roles in Catalysis

Abstract

In recent years, metal‐organic frameworks (MOFs) have gained tremendous attention as an emerging class of functional materials for the field of heterogeneous catalysis. In particular, low‐dimensionality of these material‐platforms can be singled out as an important structural parameter that endows unique or new functionalities and thus enables improved catalytic performance. Herein, firstly, this Review summarizes important development of the synthetic preparation strategies of low‐dimensional MOFs and their related composites. Next, effects of dimensionality on different catalytic roles of MOF platforms are highlighted and discussed. For instance, MOFs have been employed directly as heterogeneous catalysts, in which catalytic reactions take place within their pristine or deliberately created pores. Exploiting on the ordered pore structures, MOFs have also been integrated into reactor‐like catalysts to act as a membrane for selective catalysis. MOFs have also demonstrated to be unique support materials for other catalyst components, of which enhancement in stability and catalytic performance have been addressed. Lastly, MOFs have also been extensively utilized as a sacrificial template to derive highly porous and catalytic active nanomaterials. On the basis of our personal perspectives, some future research directions are suggested in this review in order to further advance this class of emerging catalysts.

A new 2D cadmium coordination polymer based on hydroxyl‐substituted benzenedicarboxylic acid as an effective heterogeneous catalyst for Knoevenagel condensation

“…Coordination polymers are a class of inorganic-organic hybrid materials constructed by self-assembly process of inorganic units (metal ions or clusters) and organic linkers (ligands). [1] There have been several efforts to design innovative structures in recent years to apply them for diverse applications, such as molecular sensing, [2][3][4] gas storage and separation, [5,6] dye adsorption, [7] catalysis, [8] magnetism, [9] and drug delivery. [10] Low-dimensional structures have been of considerable attention in comparison with the 3D porous frameworks, due to their easily available and accessible active sites.…”

Programmable Logic in Metal–Organic Frameworks for Catalysis

“…MOFs with specific geometric morphologies can selectively increase the number of active facets or sites, especially low dimensional MOFs, which can not only enhance the catalytic activities, but also help us understand the relationship between structure and function. [67] The modifiers (surfactants and monotopic acids) are able to impact the dimension of MOF NPs when the nucleation sites are controlled in number and prone to bind to specific crystal facets. Based on the morphology of MOF NPs obtained, three categories are divided, namely 0D, 1D, and 2D MOF NPs.…”

Rational Design of Metal–Organic Frameworks towards Efficient Electrocatalysis

“…Towards that end, lowering the dimension of MOFs to expose more active sites is believed to be effective to enhance the catalytic performance. Despite the development of zero-dimensional (0D) and one-dimensional (1D) MOFs, − constructing two-dimension (2D) MOFs are regarded as the most popular way because of the following advantages: (1) atomic thickness and 2D geometry are beneficial for rapid mass transport and fast electron transfer, (2) highly exposed catalytic active surfaces with CUSs enables high catalytic activity, and (3) the distinct surface atomic structures and bonding arrangements are easily identifiable and tunable, which provide an ideal and clear model to study the structure-property relationship of MOFs. − …”