Digital Control of Multistep Hydrothermal Synthesis by Using 3D Printed Reactionware for the Synthesis of Metal–Organic Frameworks

Abstract

Hydrothermal‐synthesis‐based reactions are normally single step owing to the difficulty of manipulating reaction mixtures at high temperatures and pressures. Herein we demonstrate a simple, cheap, and modular approach to the design reactors consisting of partitioned chambers, to achieve multi‐step synthesis under hydrothermal conditions, in digitally defined reactionware produced by 3D printing. This approach increases the number of steps that can be performed sequentially and allows an increase in the options available for the control of hydrothermal reactions. The synthetic outcomes of the multi‐stage reactions can be explored by varying reaction compositions, number of reagents, reaction steps, and reaction times, and these can be tagged to the digital blueprint. To demonstrate the potential of this approach a series of polyoxometalate (POM)‐containing metal–organic frameworks (MOFs) unavailable by “one‐pot” methods were prepared as well as a set of new MOFs.

The Research of G–Motif Construction and Chirality in Deoxyguanosine Monophosphate Nucleotide Complexes

“…Complex 5 was obtained in pure water, and the Mn(II) center is also present as a slightly distorted octahedral geometry with five coordinated water molecules and one dGMP 2– ligand by oxygen atoms and imidazole N atoms, respectively ( Figure 3 ; Supplementary Figure S12 ). The mean value of bond length Mn–O water is 2.201 (2) Å, which is in accordance with that in the previous reports ( Lin et al, 2018 ). In this complex, the symmetry-related nucleotides coordinate in the cis position.…”

Recent advances in process engineering and upcoming applications of metal–organic frameworks

“…Another factor in producibility is reaction temperature. The usual MOF synthesis involves heating of the reaction medium, and in many cases, the temperature must exceed the boiling points of the solvents [29] , [30] , [31] . Usually, water-based reactions are heated to above 100 °C and require a high-pressure reactor, called a “digestion bomb.” This approach is inadequate for large-scale production because it requires costly, large-scale, pressure-proof reactors, which decreases the producibility.…”

Automatic Generation of 3D-Printed Reactionware for Chemical Synthesis Digitization using ChemSCAD

“…To address this issue, we developed a system that exploits the standardized approach we have previously developed. 11 The Chem ical S ynthesis (by) C omputer A ided D esign (ChemSCAD) system is realized through a Python-based software application that allows the chemist to produce multistep synthesis cartridges using only parameters relevant to the synthetic procedure. This software implementation is designed to function intuitively, requiring minimal training or CAD modeling expertise.…”

“… 7 Using this approach we were able to show that 3DP reactors can be employed for a wide range of synthetic applications from flow synthesis 8 and standard batch reactions 9 to opening up new synthetic strategies in high-throughput hydrothermal synthesis. 10 , 11 Recently, we developed a standardized approach to the design and implementation of 3D printed reactors to achieve complete multistep organic and inorganic syntheses via a cartridge-based approach. 12 This led to the creation of monolithic “chemical generators”, which allowed chemical products to be obtained on-demand with minimal human intervention to achieve the desired synthesis.…”