Mechanochemical solvent-free reactions by milling, grinding or other types of mechanical action have emerged as a viable alternative to solution chemistry. Mechanochemistry offers not only a possibility to eliminate the need for bulk solvent use, and reduce the generation of waste, but it also unlocks the door to a different reaction environment in which synthetic strategies, reactions and molecules previously not accessible in solution, can be achieved. This Minireview examines the potential of mechanochemistry in chemical and materials synthesis, by providing a cross-section of the recent developments in using ball milling for the formation of molecules and materials based on covalent and coordination bonds.

Mechanochemistry for Synthesis

In recent years, mechanochemistry has been growing into a widely accepted alternative for chemical synthesis In addition to their efficiency and practicality, mechanochemical reactions are also recognized for their sustainability The association between mechanochemistry and Green Chemistry often originates from the solvent-free nature of most mechanochemical protocols, which can reduce waste production However, mechanochemistry satisfies more than one of the Principles of Green Chemistry In this Review we will present a series of examples that will clearly illustrate how mechanochemistry can significantly contribute to the fulfillment of Green Chemistry in a more holistic manner

Sustainability Assessment of Mechanochemistry by Using the Twelve Principles of Green Chemistry.

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)2(PPh3)2 as well as the commercially important metal organic frameworks (MOFs) Cu3(BTC)2 (HKUST-1), Zn(2-methylimidazolate)2 (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h−1 rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3–4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h−1. The space time yields (STYs) for these methods of up to 144 × 103 kg per m3 per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.

/pdf/synthesis-by-extrusion-continuous-large-scale-preparation-of-4ajypj1rd1.pdf

Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/ejoc.201700961

Mechanochemistry for Organic Chemists: An Update

Historically, the use of mechanochemical methods in synthesis has been almost negligible, but their perception by the synthetic community has changed in recent years and they are on their way to becoming mainstream. However, the hybridization of mechanochemical synthesis with methodologies designed to increase synthetic efficiency by allowing the generation of several bonds in a single operation has taken off only recently, but it already constitutes a very promising approach to sustainable chemistry. In this context, we provide in this Perspective a critical summary and discussion of the main known synthetic methods based on mechanochemical multicomponent reactions.

/pdf/multicomponent-mechanochemical-synthesis-3vbh46po5b.pdf

Multicomponent mechanochemical synthesis

One-pot two-step mechanochemical synthesis: ligand and complex preparation without isolating intermediates

Experimental data for air–water two-phase co-current flow in two different pipe diameters were used to test the prediction of pressure drop by a number of existing theories and correlations. Several models are shown to be useful for prediction, particularly with the stratified regimes which have proved difficult to handle in the past. The model suggested by Olujic proved to be of particular value.

Measurement and prediction of pressure drop in two‐phase flow

Although solvent-free mechanochemical synthesis continues to gain ever greater importance, the molecular scale processes that occur during such reactions remain largely uncharacterised. Here, we apply computational modelling to indentations between particles of crystals of aspirin and meloxicam under a variety of conditions to mimic the early stages of their mechanochemical cocrystallisation reaction. The study also extends to the effects of the presence of small amounts of solvent. It is found that, despite the solid crystalline nature of the reactants and the presence of little or no solvent, mixing occurs readily at the molecular level even during relatively low-energy collisions. When indented crystals are subsequently drawn apart, a connective neck formed by a mixture of the reactant molecules is observed, suggesting plastic-like behaviour of the reacting materials. Overall the work reveals some striking new insights including (i) relatively facile mixing of crystals under solvent-free conditions, (ii) no appreciable local temperature increases, (iii) localised amorphisation at the contact region and neck of the reacting crystals, and (iv) small amounts of solvent have relatively little effect during this early stage of the reaction, suggesting that their accelerating effect on the reaction may be exerted at later stages.

/pdf/insights-into-mechanochemical-reactions-at-the-molecular-16jcwkr77t.pdf

Insights into mechanochemical reactions at the molecular level: simulated indentations of aspirin and meloxicam crystals

Handle everyday research tasks with reliable, citation-backed results

Your personal Research Agent to handle research tasks with citation-backed results

Popular Tasks used by Researchers

How can I help with your research?

Meet SciSpace

Get more enhanced response by uploading the PDFs you want me to reference.

No relevant PDFs in your library

SciSpace is the AI research assistant for academics. Run systematic literature reviews on 280M+ papers, and write papers with cited sources. Trusted by 1M+ students, PhDs & researchers.

SciSpace | AI for Research

Analyze PDFs

Code & Manuscripts

Funding & Grants

Literature & Patents

Medical & Clinical Data

Systematic Review

Visualize & Present

Web & Data

Build a Google Scholar-like website for your research.

Build a website

Create charts and images for your research

Create a Chart

Write a paper for submission to a journal

Draft a manuscript

Patent Search

Design eye-catching scientific posters in minutes.

Scientific Poster Generation

Systematic Literature Review

One task is running at the moment. Your messages will be shown right after.

Drag and drop or click here to browse

Loved by <highlight>1 million+</highlight> researchers

Extract a list of specific topics and their sources from unstructured text

Topics

Compare and analyze relevant papers that matches with your search

Papers

Get insights from PDFs and bookmarked papers from your library

My library

Recent searches

Try searching for:

Catch AI-generated content in scholarly and non-scholarly content

{ai} Detector

Ai Writer

Get PDF Summaries, highlighted text explanations 

Chat with PDF

Effortlessly create in-text citations and bibliographies in APA and 2,500 other formats

Citation generator

Get explanations, summaries, and answers on academic papers

Ease up your research workflow with {scispace}'s cohort of exciting AI tools

Elevate your academic writing skills and convey your ideas the way you want

Paraphraser

Explore our range of reading and writing tools

Your file is being prepared and should be ready in a few minutes. If it's a large file, it might take a bit longer. You can close this window, and we'll email you the file when it's done.

You have reached a maximum limit of <strong>{limit}</strong> columns in the table. Remove at least <strong>1</strong> column to add or create another one.

Michael Ferguson

Author Tools

Chat about Author

Papers

One-pot two-step mechanochemical synthesis: ligand and complex preparation without isolating intermediates

Measurement and prediction of pressure drop in two‐phase flow

Insights into mechanochemical reactions at the molecular level: simulated indentations of aspirin and meloxicam crystals