Direct Z-Scheme Tannin–TiO2 Heterostructure for Photocatalytic Gold Ion Recovery from Electronic Waste

K. R. Kim, S. Choi, C. T. Yavuz, Y. S. Nam*
ACS Sustain. Chem. Eng., 8, 19, 7359–7370 (2020).
DOI: 10.1021/acsaem.0c00539

Precious-metal recovery from industrial wastewater has received considerable attention because of rapidly increasing amounts of electronic waste. Existing technologies have yet to be widely applied due to their high cost and low selectivity toward precious-metal ions. Herein, we report a direct Z-scheme tannin–TiO2 heterostructure for selective gold adsorption from electronic waste under solar irradiation. The tannin-coated TiO2 nanoparticles were prepared by a simple dipping method, and under light illumination, both tannin and TiO2 can serve as photosensitive components for the reduction of metal ions, with metal-to-ligand charge transfer from TiO2 to tannin extending the lifetime of the excited electrons. Moreover, no additional electron donors are required because the tannin layer scavenges the reactive oxygen species generated by the holes from the light-activated TiO2 surface. The heterostructure allows for the highly efficient photocatalytic recovery of gold ions, with 11 times higher adsorption capacity in the light compared to the dark. High selectivity toward gold ions was also demonstrated using a metal ion mixture including nine different metal ions that are commonly found in electronic waste. Our findings suggest that the Z-scheme heterostructure of polyphenol and semiconductor provides a promising photochemical pathway for efficient and selective metal ion recovery from electronic waste.
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Redox and Nonredox CO2 Utilization: Dry Reforming of Methane and Catalytic Cyclic Carbonate Formation

S. Subramanian, Y. Song, D. Kim, C. T. Yavuz*
ACS Energy Lett., 5, 5, 1689–1700 (2020). Invited Review
DOI: 10.1021/acsenergylett.0c00406

CO2 emissions are too large to tackle with a single process, but a combination of avoidance with chemical utilization may be able to slow global warming. In this Focus Review, we identify two large-scale CO2 conversion processes based on their viability and opposite energy requirements. In the high-energy, stationary path, CO2 reforming of methane could provide gigatons of CO2 utilization through synthesis gas. The main problem is the lack of a durable, effective, low-cost dry reforming catalyst. The exothermic cyclic carbonate formation from CO2 and organic epoxides offers a low-energy, mobile, nonredox route. The catalysts, however, must be metal-free and robust, have a high surface area, and be low-cost while being easily scalable. These two processes could potentially address at least a quarter of all current CO2 emissions.
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Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO

Y. Song, E. Ozdemir, S. Ramesh, A. Adishev, S. Subramanian, A. Harale, M. Albuali, B. A. Fadhel, A. Jamal, D. Moon, S. H. Choi, C. T. Yavuz*
Science, 367, 6479, 777-781 (2020).
DOI: 10.1126/science.aav2412

Large-scale carbon fixation requires high-volume chemicals production from carbon dioxide. Dry reforming of methane could provide an economically feasible route if coke- and sintering-resistant catalysts were developed. Here, we report a molybdenum-doped nickel nanocatalyst that is stabilized at the edges of a single-crystalline magnesium oxide (MgO) support and show quantitative production of synthesis gas from dry reforming of methane. The catalyst runs more than 850 hours of continuous operation under 60 liters per unit mass of catalyst per hour reactive gas flow with no detectable coking. Synchrotron studies also show no sintering and reveal that during activation, 2.9 nanometers as synthesized crystallites move to combine into stable 17-nanometer grains at the edges of MgO crystals above the Tammann temperature. Our findings enable an industrially and economically viable path for carbon reclamation, and the “Nanocatalysts On Single Crystal Edges” technique could lead to stable catalyst designs for many challenging reactions.

Perspective: Liyu Chen, Qiang Xu*, "Fewer defects, better catalysis?", p. 737
Research summary by Phil Szuromi, "Overcoming surface defects", p. 752-753
Highlighted in Chemistry World, C&ENNature Asia
Korean press release, English press release

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Photochemically-enhanced Selective Adsorption of Gold Ions on Tannin-coated Porous Polymer Microspheres

J. Kim, K. R. Kim, Y. Hong, S. Choi, C. T. Yavuz, J. W. Kim*, Y. S. Nam*
ACS Appl. Mater. Interfaces, 11, 24, 21915-21925 (2019).
DOI: 10.1021/acsami.9b05197

Metal recovery from electronic waste and industrial wastewater has attracted increasing attention to recycle precious metals and inhibit the emission of hazardous heavy metals. However, the selective recovery of precious metals with a large quantity is still very challenging because wastewater contains a variety of different cations while precious metal ions are relatively scarce. Here, we introduce a simple method to selectively increase the adsorption of gold ions using tannin-coated porous polymer microspheres through photochemical reduction. Mesoporous poly(ethylene glycol dimethacrylate-co-acrylonitrile) microspheres with an average pore diameter of 13.8 nm were synthesized and used as an adsorbent matrix. Tannic acid (TA) was deposited onto the internal pores of the polymer matrix by simple immersion in an aqueous milieu. TA coatings increased the maximum number of adsorbed gold ions by 1.3 times because of the well-known metal ion chelation of TA. Under light illumination, the maximum number of adsorbed gold ions dramatically increased by 6.1 times. We examined two distinct mechanisms presumably involved in the enhanced adsorption: the photooxidation of TA and plasmon-induced hot electrons. Moreover, TA-coated microspheres exhibited remarkable selectivity for gold ions among competing metal ions commonly found in waste resources. This work suggests that the photochemically activated TA can serve as an excellent adsorbent for the selective and efficient recovery of gold ions from wastewater.
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Enhanced sorption cycle stability and kinetics of CO2 on lithium silicates using lithium ion channeling effect of TiO2 nanotubes

J. S. Lee, C. T. Yavuz*
Ind. Eng. Chem. Res., accepted.
DOI: 10.1021/acs.iecr.6b04918.


Lithium silicate (Li4SiO4) is a promising high temperature CO2 sorbent because of its large CO2 capacity at elevated temperatures with low materials cost. However, the conventional nonporous Li4SiO4 shows very poor CO2 adsorption kinetics. Thus, a Li4SiO4–TiO2 nanotubes complex was synthesized where LiOH and fumed silica would be calcined around TiO2 nanotubes. TiO2 nanotubes in Li4SiO4 structure functioning as open highways, lithium ions were able to channel through the bulky structure and enhance the sorption kinetics, leading the total adsorption capacity to near theoretical values. Furthermore, cyclic studies at 700 °C revealed strong stability over at least 10 cycles. These findings indicate that stability and kinetics of CO2 sorption can be greatly improved by the nanotube composites of known adsorbents.
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Engineered nanoparticles for water treatment application

J. Byun, C. T. Yavuz*
Chapter 2 in Engineered Nanoparticles and the Environment: Biophysicochemical Processes and Toxicity, Edited by B. Xing, C. D. Vecitis, N. Senesi.
WILEY-IUPAC Series in Biophysico-Chemical Processes in Environmental Systems
Published by John Wiley & Sons, Inc.
ISBN: 9781119275824
DOI: 10.1002/9781119275855.ch2


In this chapter, water treatment processes using nanoparticles and studies related to the removal of waterborne contaminants, such as anionic, cationic, and organic pollutants, will be reviewed.
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Nanoporous Networks as Caging Supports for Uniform, Surfactant-free Co3O4 Nanocrystals and Their Applications in Energy Storage and Conversion

J. Byun, H. A. Patel, D. J. Kim, C. H. Jung, J. Y. Park*, J. W. Choi*, C. T. Yavuz* 
J. Mater. Chem. A, 3, 15489 - 15497, (2015). DOI: 10.1039/C5TA02825F.
Selected among "Hot Papers of 2015"



We report a new, surfactant-free method to produce Co3O4 nanocrystals with controlled sizes and high dispersity by caging templation of nanoporous networks. The morphologies of Co3O4 nanoparticles differ from wires to particulates by simply varying solvents. The composites of nanoparticles within network polymers are highly porous and are promising for many applications where accessible surface and aggregation prevention are important. The electrochemical performance of the composites demonstrates superior capacity and cyclic stability at a high current density (∼980 mA h g−1 at the 60th cycle at a current density of 1000 mA g−1). In a catalytic oxidation reaction of carbon monoxide, the composites exhibit a remarkable stability (in excess of 35 hours) and catalytic performance (T100 = 100 °C).
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A Half Millimeter Thick Coplanar Flexible Battery with Wireless Recharging Capability

J. S. Kim, D. Ko, D. J. Yoo, D. S. Jung, C. T. Yavuz, N. I. Kim, I. S. Choi, J. Y. Song*, J. W. Choi*
Nano Lett., 15 (4), 2350–2357, (2015). DOI: 10.1021/nl5045814.
Most read paper in March 2015.



Most of the existing flexible lithium ion batteries (LIBs) adopt the conventional cofacial cell configuration where anode, separator, and cathode are sequentially stacked and so have difficulty in the integration with emerging thin LIB applications, such as smart cards and medical patches. In order to overcome this shortcoming, herein, we report a coplanar cell structure in which anodes and cathodes are interdigitatedly positioned on the same plane. The coplanar electrode design brings advantages of enhanced bending tolerance and capability of increasing the cell voltage by in series-connection of multiple single-cells in addition to its suitability for the thickness reduction. On the basis of these structural benefits, we develop a coplanar flexible LIB that delivers 7.4 V with an entire cell thickness below 0.5 mm while preserving stable electrochemical performance throughout 5000 (un)bending cycles (bending radius = 5 mm). Also, even the pouch case serves as barriers between anodes and cathodes to prevent Li dendrite growth and short-circuit formation while saving the thickness. Furthermore, for convenient practical use wireless charging via inductive electromagnetic energy transfer and solar cell integration is demonstrated.
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Magnetic BaFe12O19 nanofiber filter for effective separation of Fe3O4 nanoparticles and removal of arsenic

J. Byun, H. A. Patel, C. T. Yavuz*
J. Nanopart. Res., 16:2787 (2014). [DOI]


Magnetic nanoparticles are promising in applications where magnetic separation is intended, although material losses via leaching mechanisms are often inevitable. Magnetic separations with widely available permanent magnets can effectively trap particles, leading to a complete removal of used or waste particles. In this report, we first demonstrate the synthesis of the thinnest (112.7 ± 16.4 nm) and most magnetic (71.96 emu g−1) barium hexaferrite (BaFe12O19, BHF—fridge magnet) via an organic solvent-free electrospinning procedure. When the fibers are then packed into a column, they clearly remove 12 nm magnetite (Fe3O4) nanoparticles quantitatively. The same BHF cartridge also removes more than 99.9 % As-treated magnetite nanoparticles at capacities up to 70 times of its weight. As a result, one liter of 150 μg L−1 As-contaminated water can be purified rapidly at a material cost of less than 2 US cents.


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A Novel, Reactive Green Iron Sulfide (Sulfide Green Rust) Formed on Iron Oxide Nanocrystals

C. Jones, S. Chattopadhyay, N. I. Gonzalez-Pech, C. Avendano, N. Hwang, S. S. Lee, M. Cho, A. Ozarowski, A. Prakash, J. T. Mayo, C. T. Yavuz, V. L. Colvin*
Chem. Mater., 27 (3), 700-707 (2015). DOI: 10.1021/cm5028942.



Iron oxide nanocrystals are of great scientific and technological interest. In this work, these materials are the starting point for producing a reactive nanoparticle whose surface resembles that of natural green rusts. Treatment of iron oxide nanoparticles with cysteamine leads to the reduction of iron and the formation of a brilliant green aqueous solution of nanocrystals rich in iron(II). These materials remained crystalline with magnetic and structural features of the original iron oxide. However, new low-angle X-ray diffraction peaks as well as vibrational features characteristic of cysteamine were found in the nanocrystalline product. X-ray absorption spectroscopy (XAS), X-ray photoemission (XPS) and Mössbauer spectroscopies indicated the presence of an iron(II)-rich phase with high sulfur content analogous to the iron–oxygen structures found in natural green rusts. Electron microscopy found that these structural components remained associated with the nonreduced iron oxide cores. These sulfur-rich analogs of natural green rusts are highly reactive and were able to rapidly degrade a model organic dye in water. This observation suggests possible actuation with a cysteamine treatment of inert and magnetic iron oxide particles at the point-of-use for environmental remediation.
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Phosphorus stimulated unidirectional growth of TiO2 nanostructures

L. White, M. Kim, J. Zhang, S. Kraemer, C. T. Yavuz, M. Moskovits, A. M. Wodtke, G. D. Stucky*
J. Mater. Chem. A, 1, 6091-6098, (2013). [DOI] [pdf] [WOS]



Previously reported TiO2 nanowire fabrication from Ni catalysts shows a surprising amount of phosphorous (P) contamination incorporated into the seed particle. We proposed this unintentional P-doping of Ni particles aids the mechanism for nanowire growth and occurs by an alternative pathway from the Vapor–Liquid–Solid (VLS) mechanism. To confirm this new mechanism, mixed phase NiP/Ni2P (NixPy) and Ni2P nanoparticles were fabricated and the central role of phosphorous in TiO2 nanowire synthesis confirmed. This newly developed P-assisted fabrication method yielded crystalline rutile TiO2 nanowires. In this mechanism solid, quasi-spherical catalyst particles attached to the ends of nanowires and surrounded by a Ni/P liquid shell are responsible for the nanowire growth. The growing end of the nanowire appears to form a “tangent-plane” to the solid catalyst core with the liquid shell wetting and occupying the interstice between the catalyst and the nanowire. In NixPy assisted growth, nanowire diameters occurred as small as 12.3 nm, some of the thinnest yet reported TiO2 nanowires resulting from atmospheric-pressure chemical vapor deposition (APCVD) growth.
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Arsenic removal by magnetic nanocrystalline barium hexaferrite

H. A. Patel, J. Byun, C. T. Yavuz*
J. Nanopart. Res., 14 (7), 881 (2012). [DOI] [pdf]

Nanoscale magnetite (Fe3O4) (15 nm) is known to remove arsenic efficiently but is very difficult to separate or require high magnetic fields to separate out from the waste water after treatment. Anisotropic hexagonal ferrite (BaFe12O19, BHF) is a well-known permanent magnet (i.e., fridge magnets) and attractive due to its low cost in making large quantities. BHF offers a viable alternative to magnetite nanocrystals for arsenic removal since it features surfaces similar to iron oxides but with much enhanced magnetism. Herein, we employ BHF nanocrystalline materials for the first time in arsenic removal from wastewater. Our results show better (75 %) arsenic removal than magnetite of the similar sizes. The BHF nanoparticles, 6.06 ± 0.52 nm synthesized by thermolysis method at 320 °C do not show hexagonal phase, however, subsequent annealing at 750 °C produced pure hexagonal BHF in 200 nm assemblies. By using BHF, we demonstrate that nanoparticle removal is more efficient and fixed bed type cartridge applications are more possible.
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One-pot facile synthesis of PEGylated Au nanoparticles in an aqueous media

S. T. Camli, F. Buyukserin, C. T. Yavuz, M. S. Yavuz*
Mater. Chem. Phys., 134 (2–3), 1153–1159, (2012). [DOI] [pdf]


We describe a facile protocol for the synthesis of PEGylated Au nanoparticles by simply mixing aqueous solutions of HAuCl4 and oligo(ethylene glycol) ethyl ether methacrylate. This method was applied to generate uniform multiply-twinned Au nanostructures of ∼21 nm in diameter with high yields. Our proposed mechanism indicates that the generation of primary alcohol intermediates from the nucleophilic addition reaction of water (nucleophile) with AuIII–vinyl complex is responsible for the reduction of gold ions. This protocol was also used to synthesize Ag nanoparticles and small aggregates of Pd nanoparticles. Due to the exclusion of sophisticated synthesis of PEG containing stabilizers, additional surfactants, or reducing agents, this approach provides a remarkably simple, versatile, and environmentally benign protocol to prepare PEGylated noble-metal nanocrystals. A comparative BSA adsorption study proved the lack of non-specific binding, a common obstacle in designing biocompatible nanoparticles.
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A multiplexed separation of iron oxide nanocrystals using variable magnetic fields

J. T. Mayo, S. S. Lee, C. T. Yavuz, W. W. Yu, A. Prakash, J. C. Falkner, V. L. Colvin*
Nanoscale, 3, 4560-4563 (2011). [DOI] [pdf]


The size-dependent magnetic properties of nanocrystals are exploited in a separation process that distinguishes particles based on their diameter. By varying the magnetic field strength, four populations of magnetic materials were isolated from a mixture. This separation is most effective for nanocrystals with diameters between 4 and 16 nm.



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In situ real time monitoring of Pt-VO2 nanoparticle-nanowire assembly by GISAXS

C. T. Yavuz*, S. Lee, B. Lee, M. H. Kim, J. M. Baik, C. Larson, S. Seifert, S. Vajda, R. E. Winans, M. Moskovits, G. D. Stucky, A. M. Wodtke
Proc. SPIE, Vol. 7679, 76792D (2010). [DOI] [pdf]

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Pd-sensitized single vanadium oxide nanowires: highly-responsive hydrogen sensing based on the Mott transition

J. M. Baik, M. H. Kim, C. Larson, C. T. Yavuz, G. D. Stucky, A. M. Wodtke, M. Moskovits*
Nano Lett., 9 (12), 3980–3984 (2009). [DOI] [pdf]

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Growth of metal oxide nanowires from supercooled liquid nanodroplets

M. H. Kim, B. Lee, S. Lee, C. Larson, J. M. Baik, C. T. Yavuz, S. Seifert, S. Vajda, R. E. Winans, M. Moskovits, G. D. Stucky, A. M. Wodtke*
Nano Lett. 9 (12), 4138–4146 (2009). [DOI] [pdf]

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Pollution Magnet: Nano Magnetite for Arsenic Removal from Drinking Water

C. T. Yavuz, J. T. Mayo, C. Suchecki, J. Wang, A. Z. Ellsworth, H. D’Couto, E. Quevedo, A. Prakash, L. Gonzalez, C. Nguyen, C. Kelty, V. L. Colvin*
Environ. Geochem. Health, 32, 327–334 (2010). [DOI] [pdf]

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Applying analytical ultracentrifugation to nanocrystal suspensions

J. A. Jamison, K. M. Krueger, J. T. Mayo, C. T. Yavuz, J. J. Redden, V. L. Colvin*
Nanotechnology, 20, 355702-12, (2009). [DOI] [pdf]
Image from NETL
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Size-dependent sedimentation properties of nanocrystals

J. A. Jamison, K. M. Krueger, C. T. Yavuz, J. T. Mayo, D. LeCrone, J. J. Redden, V. L. Colvin*
ACS Nano, 2, 311-319 (2008). [DOI] [pdf]

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