The application of high pressure favors many chemical processes, providing higher yields or improved rates in chemical reactions and improved solvent power in separation processes, and allowing activation barriers to ...The application of high pressure favors many chemical processes, providing higher yields or improved rates in chemical reactions and improved solvent power in separation processes, and allowing activation barriers to be overcome through the increase in molecular energy and molecular collision rates. High pressures-up to millions of bars using diamond anvil cells-can be achieved in the laboratory, and lead to many new routes for chemical synthesis and the synthesis of new materials with desirable thermody- namic, transport, and electronic properties. On the industrial scale, however, high-pressure processing is currently limited by the cost of compression and by materials limitations, so that few industrial processes are carried out at pressures above 25 MPa. An alternative approach to high-pressure processing is pro- posed here, in which very high local pressures are generated using the surface-driven interactions from a solid substrate. Recent experiments and molecular simulations show that such interactions can lead to local pressures as high as tens of thousands of bars (1 bar=1×10^5 Pa), and even millions of bars in some cases. Since the active high-pressure processing zone is inhomogeneous, the pressure is different in dif- ferent directions. In many cases, it is the pressure in the direction parallel to the surface of the substrate (the tangential pressure) that is most greatly enhanced. This pressure is exerted on the molecules to be processed, but not on the solid substrate or the containing vessel. Current knowledge of such pressure enhancement is reviewed, and the possibility of an alternative route to high-pressure processing based on surface-driven forces is discussed. Such surface-driven high-pressure processing would have the advantage of achieving much higher pressures than are possible with traditional bulk-phase processing, since it eliminates the need for mechanical compression. Moreover, no increased pressure is exerted on the containing vessel for the process, thus eliminating concerns about materials failure.展开更多
基金the US National Science Foundation (CBET-1603851 and CHE-1710102) for support of this workthe National Science Center of Poland (DEC-2013/09/B/ST4/03711) for support
文摘The application of high pressure favors many chemical processes, providing higher yields or improved rates in chemical reactions and improved solvent power in separation processes, and allowing activation barriers to be overcome through the increase in molecular energy and molecular collision rates. High pressures-up to millions of bars using diamond anvil cells-can be achieved in the laboratory, and lead to many new routes for chemical synthesis and the synthesis of new materials with desirable thermody- namic, transport, and electronic properties. On the industrial scale, however, high-pressure processing is currently limited by the cost of compression and by materials limitations, so that few industrial processes are carried out at pressures above 25 MPa. An alternative approach to high-pressure processing is pro- posed here, in which very high local pressures are generated using the surface-driven interactions from a solid substrate. Recent experiments and molecular simulations show that such interactions can lead to local pressures as high as tens of thousands of bars (1 bar=1×10^5 Pa), and even millions of bars in some cases. Since the active high-pressure processing zone is inhomogeneous, the pressure is different in dif- ferent directions. In many cases, it is the pressure in the direction parallel to the surface of the substrate (the tangential pressure) that is most greatly enhanced. This pressure is exerted on the molecules to be processed, but not on the solid substrate or the containing vessel. Current knowledge of such pressure enhancement is reviewed, and the possibility of an alternative route to high-pressure processing based on surface-driven forces is discussed. Such surface-driven high-pressure processing would have the advantage of achieving much higher pressures than are possible with traditional bulk-phase processing, since it eliminates the need for mechanical compression. Moreover, no increased pressure is exerted on the containing vessel for the process, thus eliminating concerns about materials failure.