Low-Valence Metal Single Atoms on Graphdiyne Promotes Electrochemical Nitrogen Reduction via M-to-N 2 π-Backdonation
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99 GENERAL AND MISCELLANEOUS↗
Engineering topics
Tang, Chao
Publications and source records attributed to Tang, Chao.
Ion Separations Based on Spontaneously Arising Streaming Potentials in Rotating Isoporous Membranes
Highly selective ion separations are vital for producing pure salts, and membrane-based separations are promising alternatives to conventional ion-separation techniques. Our previous work demonstrated that simple pressure-driven flow through negatively charged isoporous membranes can separate Li+ and K+ with selectivities as high as 70 in dilute solutions. The separation mechanism relies on spontaneously arising streaming potentials that induce electromigration, which opposes advection and separates cations based on differences in their electrophoretic mobilities. Although the separation technique is simple, this work shows that high selectivities are possible only with careful consideration of experimental conditions including transmembrane pressure, solution ionic strength, the K+/Li+ ratio in the feed, and the extent of concentration polarization. Separations conducted with a rotating membrane show Li+/K+ selectivities as high as 150 with a 1000 rpm membrane rotation rate, but the selectivity decreases to 1.3 at 95 rpm. These results demonstrate the benefits and necessity of quantitative control of concentration polarization in highly selective separations. Increases in solution ionic strength or the K+/Li+ feed ratio can also decrease selectivities more than an order of magnitude.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Few-Atom Copper Catalyst for the Electrochemical Reduction of CO to Acetate: Synergetic Catalysis between Neighboring Cu Atoms
Single-atom catalysts (SACs) are gaining increasing recognition because of their superior catalytic properties for various reactions. However, the performance of SACs is often limited by the lack of neighboring metal centers to cooperate in catalysis. Herein, a synergetic interaction between neighboring Cu atoms of a few-atom catalyst (FAC) on graphdiyne is found to greatly enhance the production of acetate in CO electroreduction reaction relative to Cu SACs. In a 1.0 M KOH electrolyte, this Cu FAC exhibits an acetate Faradaic efficiency of 53.8±1.5 % and an ultrahigh relative purity of up to 97 wt% for liquid products, and excellent stability of over 23 h continuous electrolysis at -0.8 V versus reversible hydrogen electrode (RHE). Theoretical studies suggest that the intersite catalytic communication between two neighboring metal atoms confined in each pore of GDY facilitates the formation of acetic acid through either stepwise hydrogenation of CH 2 CO* or the direct reaction of H 2 O with CH 2 CO*. Our study demonstrates the unprecedented synergetic catalysis of Cu FAC in promoting the selective CO electroreduction toward acetate production.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Highly selective ion separations based on counter-flow electromigration in nanoporous membranes
Highly selective ion separations are vital for recovering important salts, and membrane-based techniques may enable environmentally friendly ion separations that operate continuously. This study demonstrates that simply opposing convective flow with electromigration in track-etched membranes leads to remarkable selectivities among monovalent ions. Because the membrane-pore diameters are orders of magnitude larger than the ion diameters, advection moves all ions at the same velocity, whereas electrophoretic velocities are proportional to ion mobilities. Thus during counter-flow cation electromigration, less mobile cations have lower electromigration velocity components and pass through porous membranes more rapidly than more mobile cations. Using membranes with 400 nm pores, counter-flow electromigration gives Li + /K + selectivities of 100 and Li + /Na + selectivities around 30 in mixed-salt studies. In this work, numerical simulations based on the extended Nernst-Planck equation agree with trends in experimental data and highlight the importance of high Péclet numbers, high current-to-flow ratios, and uniform current distributions for achieving high selectivities. Importantly, experimental separations give high selectivities at 0.3 M ionic strength and low Li + /K + ratios, which suggest these methods may also work in brine solutions. Nevertheless, energy costs for such separations are high.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ion separations with membranes
Ion separations are important for resource recovery, water treatment, and energy production and storage. Techniques such as chemical precipitation, selective adsorption, and solvent extraction are effective, but membranes may separate ions continuously with less waste and lower energy costs. Separation of monovalent and multivalent ions with nanofiltration or electrodialysis membranes already enables water softening and edible salt purification. Similar membranes are attractive as separators in vanadium redox flow batteries. Selective partitioning of divalent counter-ions into ion-exchange membranes even allows transport of these ions against their concentration gradients in salt mixtures. However, separations of ions with the same charge is more challenging. Recent research demonstrated highly selective ion “sieving” at small scales. Here, separations using electrical potentials and differences in ion electrophoretic mobilities are promising, but relatively unexplored. Carrier-mediated transport affords high selectivity in liquid membranes, but these systems are not very stable, and selective transport via hopping between anchored carriers has proven elusive. Finally, this paper discusses how concentration polarization decreases selectivities in many membrane processes. Although development of selective, inexpensive ion-separation membranes is a work in progress, successes in water softening and edible salt purification suggests that future selective membranes will serve as complementary methods to traditional purification techniques.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Flow through negatively charged, nanoporous membranes separates Li + and K + due to induced electromigration
Flow through negatively charged nanopores separates Li + and K + with selectivities of up to 70 and Li + passages from 20% to above 100%. Remarkably, both the Li + /K + selectivity and Li + passage initially increase with flow rate, breaking the permeability/selectivity trade-off. Modelling demonstrates that flow through the membranes creates electric fields that retard transport of cations. Selectivity increases with flow rate because the K + electromigration velocity exceeds its convective velocity, but for Li + electromigration is weaker than convection. Here, modelling also shows the importance of controlling concentration polarization. With further work, related separations might provide highly pure Li salts for battery manufacturing.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Droplet model for autocorrelation functions in an Ising ferromagnet
The autocorrelation function of Ising spins in an ordered phase is studied via a droplet model. Only noninteracting spherical droplets are considered. The Langevin equation which describes fluctuations in the radius of a single droplet is studied in detail. A general description of the transformation to a Fokker-Planck equations and the ways in which a spectral analysis of that equation can be used to compute the autocorrelation function is given. It is shown that the eigenvalues of the Fokker-Planck operator form (1) a continuous spectrum of relaxation rates starting from zero for d = 2, (2) a continuous spectrum with a finite gap for d = 3, and (3) a discrete spectrum for d greater than 4, where d is the spatial dimensionality. Detailed solutions for various cases are presented.
Tang, Chao↗
Critical exponents and scaling relations for self-organized critical phenomena
Critical indices beta, gamma delta, nv, etc. are defined and calculated for self-organized critical phenomena. Scaling relations are derived and checked numerically. The order-parameter exponent beta describes the spontaneous current and the relaxation to the criticl point. The power spectrum has 'l/f' behavior with the exponent phi = nv x z, where z is the dynamical critical exponent.
Tang, Chao↗