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Nanochemistry Views Geoffrey A Nanochemistry Views Geoffrey A. Ozin Nanochemistry Views Geoffrey A. Ozin Materials Chemistry and Nanochemistry Research Group, Center for Inorganic and Polymeric Nanomaterials, Chemistry Department, 80 St. George Street, University of Toronto, Toronto, Ontario, Canada M5S 3H6 After more than four and a half decades of research in the field of nanochemistry I was given the interesting opportunity to write a monthly opinion editorial for the Nano Materials Views section of the VCH-Wiley materials journals, Advanced Science, Advanced Materials, Advanced Functional Materials, Small, Particle, Advanced Engineering Materials, Advanced Optical Materials and Advanced Health Materials. This chance provided me with a superb vehicle to express opinionated and provocative views about hot button issues in nanochemistry. Dreaming up and composing these editorials has been a valuable lesson in how to write scientifically, technologically and politically correct critiques about controversial topics for a public forum, a pastime less risky for a senior scientist than a junior one. After having produced 36 of these opinion editorials on a variety of contemporary topics in nanochemistry, I thought it worthwhile to integrate them into a compendium of essays in the form of a monograph entitled Nanochemistry Views as a three score years and ten plus one, milestone in my life. I hope the reader enjoys these stories as much as I had fun writing them and at the same time learning much from knowledgeable colleagues who contributed insightful and important commentaries on my opinions, sometimes voicing heterodox views, many of which in anonymous form I included in much improved final drafts. I also received terrifically helpful editing on more-or-less every story from my talented and dynamic group of co-workers as well as excellent artistic renditions of the content of many of the stories from Wendong Wang, Chenxi Qian and ArtScientist Todd Siler. Geoffrey A Ozin Toronto 2012 Geoffrey Ozin – Brief Biographical Geoffrey Ozin is renowned for his pioneering research in nanochemistry. His work has defined, enabled and popularized a chemical approach to nanomaterials, a rapidly expanding field, a cornerstone of modern chemistry and a foundation for innovative nanotechnology in advanced materials and biomedical science. Four and a half decades of ground-breaking interdisciplinary research on nanomaterials established Geoffrey Ozin as one of the “founding fathers of nanochemistry.” This emerging and dynamic interdisciplinary field is an essential driver of the 21st century nanotechnology revolution. He was there in the 1970s at the birthing of the science that is now called nanochemistry, which synthesizes nanoscale structures and integrated nanosystems from the bottom up, literally atom-by-atom. Today nanometer- scale matter and voids are the central building blocks of nanoscience and the groundbreaking works of Geoffrey Ozin in wide-ranging fields, briefly summarized below, provided the spark that helped make it happen. 1970s: Matrix isolation laser Raman spectroscopy – Pioneering experiments on inorganic, organometallic and cluster reactive intermediates. Naked metal clusters – “Atom-by-atom” investigations of the controlled nucleation and growth of “ligand-free” metal clusters enabled the earliest insight into the fuzzy interface between molecular nanoclusters and quantum confined nanocrystals. Chemistry of naked metal clusters – “Atom-by-molecule” investigations of the reaction of small molecules with controlled-nuclearity ligand-free metal clusters provided archetype “chemisorption models” for the same molecules chemisorbed on metal surfaces. Naked metal atom and metal cluster photochemistry – Pioneering studies of metal atom photo-aggregation, metal cluster photo-dissociation, metal cluster photo-isomerization and metal-atom photo-insertion into the C-H bond of methane. 1980s: Nanoporous materials chemistry – Enabled the transition of the field of zeolite science from its traditional focus on catalysis and gas separation into the world of advanced nanoporous materials science with objectives centered on novel solid state devices where molecule size and shape recognition and discrimination matters. Biomimetic nanomaterials – Transferred some of nature’s best biomaterials ideas in the nanochemistry laboratory to originate the area of “morphosynthesis”, a self-assembly paradigm inspired by “morphogenesis” in the natural world, exemplified by the synthesis of faux diatoms and radiolarian, hollow helicoids and rounded figurines. 1990s: Hybrid nanomaterials – Invented an entirely new class of nanocomposites, dubbed periodic mesoporous organosilicas, PMOs, with bridge-bonded organic molecules uniquely imprinted in the inorganic pore walls, creating materials properties that transcend the sum of the inorganic and organic components, finding widespread applications in microelectronics, catalysis, chromatography, dental implants and drug delivery. Host-guest nanomaterials – Among the first to synthesize size, shape and surface controlled insulating, semiconducting and metallic nanomaterials, nucleated, grown, stabilized and protected within the spatial confines of nanoporous hosts. 2000s: Mesoscopic materials – Pioneering research on the growth and form of self-assembled materials with structural features spanning nanoscopic to macroscopic scales, exemplified by spheres, wires, rods, tubes, helices and films, a “panoscopic” or “hierarchical” view of self-assembling materials. Photonic crystal materials – Chemistry approach to the world’s first synthetic three-dimensional silicon photonic crystal with a complete photonic bandgap at optical telecom wavelengths. This research initiated the field of tunable photonic color materials and evolved to award winning nanotechnology platforms being commercialized by the spin-off company www.Opalux.com. Slow photons in chemistry – Proof-of-concept research that demonstrated slow light localized at the photonic band edges of synthetic photonic crystals made of photocatalytic materials can speed up the rates of light driven chemical reactions, exemplified by organic photoisomerizations and organic photooxidations. Nanolocomotion – Among the first few scientists to demonstrate chemically powered ‘nanolocomotion’ based on chemical control of the motion of segmented barcode nanorod motors, whose power is obtained from the decomposition of hydrogen peroxide into water and oxygen localized at the catalytic segment of the nanorod. This work has inspired a veritable ‘nanomotor industry’. Nanochemistry education - The textbooks ‘Concepts in Nanochemistry’ and ‘Nanochemistry’, co-authored with former students Andre Arsenault and Ludovico Cademartiri, are the globally acclaimed academic and industry gold standard written resources for teaching and practicing a chemical approach to nanomaterials. 2010s: Ultrathin inorganic nanowires – Discovery of ultrathin bismuth sesquisulfide Bi2S3 nanowires with an unprecedented small diameter of 1.6 nm. This work inspired a flurry of activity around the globe to explore the composition, structure and property space of these uniquely thin one- dimensional nanomaterials. Green nanochemistry – Separation of poly- dispersions of non-toxic, quantum confined silicon nanocrystals into mono- disperse colloidally-stable fractions with tailored organic surfaces and bright, size-tunable visible to near infrared photoluminescence, provided their size- dependent chemical, physical and biological properties, creating opportunities for the development of novel advanced materials and biomedical devices. Solar Fuels – Research aimed at exploiting the boundless energy of the sun to make fuels and chemicals from abundant greenhouse gas carbon dioxide rather than the current practice of continuing to deplete our legacy fossil fuels, the ultimate goal being an energy transition from an unsustainable fossil fuels based economy to a sustainable one founded on solar fuels. Contents 1. Life before Advanced Materials? 2. Is the Nano-Bubble about To Burst? 3. The Good Nano Stuff - Where Is It Going? 4. Nano Silicon Samurai? 5. Who Needs A NanoScientist? 6. What Can Nanochemistry do for Hydrogen Storage? 7. Natural Nanochemistry: Artificial Petrification 8. Nanochemistry: Who Owns It? 9. What can Nanochemistry do for Photonic Metamaterials? 10. Nanochemistry Pores For Thought 11. Powering the Planet with Energy Nanomaterials? 12. Nanospheres and Solar Cells – On a Roll 13. What can Nanochemistry do for Chemical and Biochemical Sensing? 14. Bragging About Nanoparticles 15. Artificial Photosynthesis versus Greenhouse Gas 16. How “Green” Does Your Nano Materials Garden Grow? 17. What Is My (Nano)Material Good For ? 18. Nanochemistry Nostalgia 2011 19. Ode to CO2 20. Nanochemistry: Prescience? 21. Nature’s Nanomaterials – To Be or Not to Be Bioinspired? 22. Spin of a Nanotech Spin off 23. Evolutionary Nanochemistry 24. Tribute to Richard Barrer 25. Nanomaterials Kaleidoscope – Building a Nanochemistry Periodic Table 26. Fuel from the Sun 27. Climate Confusion 28. Nanochemistry Reproducibility 29. Exploring the Possibilities and Limitations of a Nanomaterials Genome 30. Todd Siler’s Nano World – Think Billionths of a Meter 31. A Fossil Fuel Free World 32. Real or Artifact: CO2 Photo-Catalysis versus Carbon Contamination 33. Is Semiconductor Photocatalysis Photochemical or Thermochemical or Both and do we Care? 34. This is your Brain on Art 35. Do we have a Plan B? 36. Jarring Fears – Have We Covered Everything? 37. CO2: War
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