@article{ElNagarSarhanAbouserieetal.2017, author = {El-Nagar, Gumaa A. and Sarhan, Radwan Mohamed and Abouserie, Ahed and Maticiuc, Natalia and Bargheer, Matias and Lauermann, Iver and Roth, Christina}, title = {Efficient 3D-Silver Flower-like Microstructures for Non-Enzymatic Hydrogen Peroxide (H2O2) Amperometric Detection}, series = {Scientific reports}, volume = {7}, journal = {Scientific reports}, publisher = {Nature Publ. Group}, address = {London}, issn = {2045-2322}, doi = {10.1038/s41598-017-11965-9}, pages = {8}, year = {2017}, language = {en} } @article{ElNagarLauermannSarhanetal.2018, author = {El-Nagar, Gumaa A. and Lauermann, Iver and Sarhan, Radwan Mohamed and Roth, Christina}, title = {Hierarchically structured iron-doped silver (Ag-Fe) lotus flowers for an efficient oxygen reduction reaction}, series = {Nanoscale}, volume = {10}, journal = {Nanoscale}, number = {15}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2040-3364}, doi = {10.1039/c8nr00020d}, pages = {7304 -- 7310}, year = {2018}, abstract = {The development of cheap and efficient electrocatalysts for the oxygen reduction reaction (ORR) is vital for the immediate commercialization of fuel cells which are still limited by the high cost and low performance of the utilized commercial Pt-based electrodes. As a promising alternative, this study reports on the synthesis of hierarchical iron-doped silver lotus flowers (AgFelotus) by a facile chemical procedure as robust and efficient ORR electrocatalysts. Succinic acid was used as a structure directing agent to tune the morphology of undoped and iron-doped silver particles. In the absence of succinic acid, ball-like silver particles were obtained, while using 2 mM succinic acid led to peony-like flower structures. The doping of silver peony-flowers with iron resulted in lotus-like flower structures with high electrocatalytic activity for ORR together with outstanding tolerance against poisoning with various hydrocarbon (HC) impurities, in situ generated during fuel cell operation, as well as different fuels from anodic crossover. AgFelotus exhibited a superior ORR activity with more than 40 times higher stability than the commercial Pt/C catalyst in alkaline media. This substantial performance enhancement is attributed to the unique lotus-like flower structures providing more electroactive surface sites, in addition to the iron dopants which facilitate ORR charge transfer.}, language = {en} } @article{LiebigSarhanPrietzeletal.2018, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Th{\"u}nemann, Andreas F. and Bargheer, Matias and Koetz, Joachim}, title = {Undulated Gold Nanoplatelet Superstructures}, series = {Langmuir}, volume = {34}, journal = {Langmuir}, number = {15}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.7b02898}, pages = {4584 -- 4594}, year = {2018}, abstract = {Negatively charged flat gold nanotriangles, formed in a vesicular template phase and separated by an AOT-micelle-based depletion flocculation, were reloaded by adding a cationic polyelectrolyte, that is, a hyperbranched polyethylenimine (PEI). Heating the system to 100 degrees C in the presence of a gold chloride solution, the reduction process leads to the formation of gold nanoparticles inside the polymer shell surrounding the nanoplatelets. The gold nanoparticle formation is investigated by UV-vis spectroscopy, small-angle X-ray scattering, and dynamic light scattering measurements in combination with transmission electron microscopy. Spontaneously formed gold clusters in the hyperbranched PEI shell with an absorption maximum at 350 nm grow on the surface of the nanotriangles as hemispherical particles with diameters of similar to 6 nm. High-resolution micrographs show that the hemispherical gold particles are crystallized onto the {111} facets on the bottom and top of the platelet as well as on the edges without a grain boundary. Undulated gold nanoplatelet superstructures with special properties become available, which show a significantly modified performance in SERS-detected photocatalysis regarding both reactivity and enhancement factor.}, language = {en} } @misc{LiebigSarhanBargheeretal.2020, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Bargheer, Matias and Schmitt, Clemens Nikolaus Zeno and Poghosyan, Armen H. and Shahinyanf, Aram A. and Koetz, Joachim}, title = {Spiked gold nanotriangles}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch Naturwissenschaftliche Reihe}, number = {829}, issn = {1866-8372}, doi = {10.25932/publishup-44556}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-445568}, pages = {11}, year = {2020}, abstract = {We show the formation of metallic spikes on the surface of gold nanotriangles (AuNTs) by using the same reduction process which has been used for the synthesis of gold nanostars. We confirm that silver nitrate operates as a shape-directing agent in combination with ascorbic acid as the reducing agent and investigate the mechanism by dissecting the contribution of each component, i.e., anionic surfactant dioctyl sodium sulfosuccinate (AOT), ascorbic acid (AA), and AgNO3. Molecular dynamics (MD) simulations show that AA attaches to the AOT bilayer of nanotriangles, and covers the surface of gold clusters, which is of special relevance for the spike formation process at the AuNT surface. The surface modification goes hand in hand with a change of the optical properties. The increased thickness of the triangles and a sizeable fraction of silver atoms covering the spikes lead to a blue-shift of the intense near infrared absorption of the AuNTs. The sponge-like spiky surface increases both the surface enhanced Raman scattering (SERS) cross section of the particles and the photo-catalytic activity in comparison with the unmodified triangles, which is exemplified by the plasmon-driven dimerization of 4-nitrothiophenol (4-NTP) to 4,4'-dimercaptoazobenzene (DMAB).}, language = {en} } @article{LiebigHenningSarhanetal.2018, author = {Liebig, Ferenc and Henning, Ricky and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Bargheer, Matias and Koetz, Joachim}, title = {A new route to gold nanoflowers}, series = {Nanotechnology}, volume = {29}, journal = {Nanotechnology}, number = {18}, publisher = {IOP Publ. Ltd.}, address = {Bristol}, issn = {0957-4484}, doi = {10.1088/1361-6528/aaaffd}, pages = {8}, year = {2018}, abstract = {Catanionic vesicles spontaneously formed by mixing the anionic surfactant bis(2-ethylhexyl)sulfosuccinate sodium salt with the cationic surfactant cetyltrimethylammonium bromide were used as a reducing medium to produce gold clusters, which are embedded and well-ordered into the template phase. The gold clusters can be used as seeds in the growth process that follows by adding ascorbic acid as a mild reducing component. When the ascorbic acid was added very slowly in an ice bath round-edged gold nanoflowers were produced. When the same experiments were performed at room temperature in the presence of Ag+ ions, sharp-edged nanoflowers could be synthesized. The mechanism of nanoparticle formation can be understood to be a non-diffusion-limited Ostwald ripening process of preordered gold nanoparticles embedded in catanionic vesicle fragments. Surface-enhanced Raman scattering experiments show an excellent enhancement factor of 1.7 . 10(5) for the nanoflowers deposited on a silicon wafer.}, language = {en} } @article{SarhanKoopmanPudelletal.2019, author = {Sarhan, Radwan Mohamed and Koopman, Wouter-Willem Adriaan and Pudell, Jan-Etienne and Stete, Felix and R{\"o}ssle, Matthias and Herzog, Marc and Schmitt, Clemens Nikolaus Zeno and Liebig, Ferenc and Koetz, Joachim and Bargheer, Matias}, title = {Scaling up nanoplasmon catalysis}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {123}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {14}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.8b12574}, pages = {9352 -- 9357}, year = {2019}, abstract = {Nanoscale heating by optical excitation of plasmonic nanoparticles offers a new perspective of controlling chemical reactions, where heat is not spatially uniform as in conventional macroscopic heating but strong temperature gradients exist around microscopic hot spots. In nanoplasmonics, metal particles act as a nanosource of light, heat, and energetic electrons driven by resonant excitation of their localized surface plasmon resonance. As an example of the coupling reaction of 4-nitrothiophenol into 4,4′-dimercaptoazobenzene, we show that besides the nanoscopic heat distribution at hot spots, the microscopic distribution of heat dictated by the spot size of the light focus also plays a crucial role in the design of plasmonic nanoreactors. Small sizes of laser spots enable high intensities to drive plasmon-assisted catalysis. This facilitates the observation of such reactions by surface-enhanced Raman scattering, but it challenges attempts to scale nanoplasmonic chemistry up to large areas, where the excess heat must be dissipated by one-dimensional heat transport.}, language = {en} } @misc{ElNagarLauermannSarhanetal.2019, author = {El-Nagar, Gumaa A. and Lauermann, Iver and Sarhan, Radwan Mohamed and Roth, Christina}, title = {Hierarchically structured iron-doped silver (Ag-Fe) lotus flowers for an efficient oxygen reduction reaction (vol 10, pg 7304 -7310, 2018)}, series = {Nanoscale}, volume = {11}, journal = {Nanoscale}, number = {24}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2040-3364}, doi = {10.1039/c9nr90131k}, pages = {11975 -- 11975}, year = {2019}, language = {en} } @article{SarhanElNagarAbouserieetal.2019, author = {Sarhan, Radwan Mohamed and El-Nagar, Gumaa A. and Abouserie, Ahed and Roth, Christina}, title = {Silver-Iron Hierarchical Microflowers for Highly Efficient H2O2 Nonenzymatic Amperometric Detection}, series = {ACS sustainable chemistry \& engineering}, volume = {7}, journal = {ACS sustainable chemistry \& engineering}, number = {4}, publisher = {American Chemical Society}, address = {Washington}, issn = {2168-0485}, doi = {10.1021/acssuschemeng.8b06182}, pages = {4335 -- 4342}, year = {2019}, abstract = {This study addresses the fabrication of monodispersed iron-doped silver meso-hierarchical flower-like structures via a facile chemical procedure. The morphology of the obtained silver particles has been tuned by changing the concentration of the structure-directing agent (malonic acid). Ball-shaped silver particles were formed in the absence of malonic acid (MA), while silver particles with craspedia-globosa, chrysanthemum, and dahlia flower-like structures were obtained in the presence of 0.2, 0.5, and 1 mM malonic acid, respectively. The doping of these dahlia flower-like structures with trace amounts of iron (<= 5\% Fe weight percent) led to the formation of globe-amaranth iron-doped microflowers (AgFeamaranth). The as-prepared AgFeamaranth exhibited better performance as a nonenzymatic H2O2 sensor compared to undoped silver particles as demonstrated by their higher catalytic activity and stability together with superior sensitivity (1350 mu M-1 cm(-2), 61 times higher) and lower detection limit (0.1 mu M). These enhancements are attributed to the AgFe unique flower-like structures and to the fact that the iron dopants provide a higher number of electroactive sites and reduce the charge transfer resistance of H2O2 reduction. Additionally, the good stability of AgFe is believed to originate from the faster detachment rate of the in situ-formed gas bubbles from their surfaces compared to undoped silver structures.}, language = {en} } @misc{LiebigHenningSarhanetal.2019, author = {Liebig, Ferenc and Henning, Ricky and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Schmitt, Clemens Nikolaus Zeno and Bargheer, Matias and Koetz, Joachim}, title = {A simple one-step procedure to synthesise gold nanostars in concentrated aqueous surfactant solutions}, series = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, number = {769}, issn = {1866-8372}, doi = {10.25932/publishup-43874}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-438743}, pages = {23633 -- 23641}, year = {2019}, abstract = {Due to the enhanced electromagnetic field at the tips of metal nanoparticles, the spiked structure of gold nanostars (AuNSs) is promising for surface-enhanced Raman scattering (SERS). Therefore, the challenge is the synthesis of well designed particles with sharp tips. The influence of different surfactants, i.e., dioctyl sodium sulfosuccinate (AOT), sodium dodecyl sulfate (SDS), and benzylhexadecyldimethylammonium chloride (BDAC), as well as the combination of surfactant mixtures on the formation of nanostars in the presence of Ag⁺ ions and ascorbic acid was investigated. By varying the amount of BDAC in mixed micelles the core/spike-shell morphology of the resulting AuNSs can be tuned from small cores to large ones with sharp and large spikes. The concomitant red-shift in the absorption toward the NIR region without losing the SERS enhancement enables their use for biological applications and for time-resolved spectroscopic studies of chemical reactions, which require a permanent supply with a fresh and homogeneous solution. HRTEM micrographs and energy-dispersive X-ray (EDX) experiments allow us to verify the mechanism of nanostar formation according to the silver underpotential deposition on the spike surface in combination with micelle adsorption.}, language = {en} } @article{vonReppertSarhanSteteetal.2016, author = {von Reppert, Alexander and Sarhan, Radwan Mohamed and Stete, Felix and Pudell, Jan-Etienne and Del Fatti, N. and Crut, A. and Koetz, Joachim and Liebig, Ferenc and Prietzel, Claudia Christina and Bargheer, Matias}, title = {Watching the Vibration and Cooling of Ultrathin Gold Nanotriangles by Ultrafast X-ray Diffraction}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {120}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.6b11651}, pages = {28894 -- 28899}, year = {2016}, abstract = {We study the vibrations of ultrathin gold nanotriangles upon optical excitation of the electron gas by ultrafast X-ray diffraction. We quantitatively measure the strain evolution in these highly asymmetric nano-objects, providing a direct estimation of the amplitude and phase of the excited vibrational motion. The maximal strain value is well reproduced by calculations addressing pump absorption by the nanotriangles and their resulting thermal expansion. The amplitude and phase of the out-of-plane vibration mode with 3.6 ps period dominating the observed oscillations are related to two distinct excitation mechanisms. Electronic and phonon pressures impose stresses with different time dependences. The nanosecond relaxation of the expansion yields a direct temperature sensing of the nano-object. The presence of a thin organic molecular layer at the nanotriangle/substrate interfaces drastically reduces the thermal conductance to the substrate.}, language = {en} } @article{LiebigSarhanBargheeretal.2020, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Bargheer, Matias and Schmitt, Clemens Nikolaus Zeno and Poghosyan, Armen H. and Shahinyanf, Aram A. and Koetz, Joachim}, title = {Spiked gold nanotriangles}, series = {RSC Advances}, volume = {10}, journal = {RSC Advances}, number = {14}, publisher = {RSC Publishing}, address = {London}, issn = {2046-2069}, doi = {10.1039/d0ra00729c}, pages = {8152 -- 8160}, year = {2020}, abstract = {We show the formation of metallic spikes on the surface of gold nanotriangles (AuNTs) by using the same reduction process which has been used for the synthesis of gold nanostars. We confirm that silver nitrate operates as a shape-directing agent in combination with ascorbic acid as the reducing agent and investigate the mechanism by dissecting the contribution of each component, i.e., anionic surfactant dioctyl sodium sulfosuccinate (AOT), ascorbic acid (AA), and AgNO3. Molecular dynamics (MD) simulations show that AA attaches to the AOT bilayer of nanotriangles, and covers the surface of gold clusters, which is of special relevance for the spike formation process at the AuNT surface. The surface modification goes hand in hand with a change of the optical properties. The increased thickness of the triangles and a sizeable fraction of silver atoms covering the spikes lead to a blue-shift of the intense near infrared absorption of the AuNTs. The sponge-like spiky surface increases both the surface enhanced Raman scattering (SERS) cross section of the particles and the photo-catalytic activity in comparison with the unmodified triangles, which is exemplified by the plasmon-driven dimerization of 4-nitrothiophenol (4-NTP) to 4,4'-dimercaptoazobenzene (DMAB).}, language = {en} } @article{LiebigSarhanPrietzeletal.2016, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Reinecke, Antje and Koetz, Joachim}, title = {"Green" gold nanotriangles: synthesis, purification by polyelectrolyte/micelle depletion flocculation and performance in surface-enhanced Raman scattering}, series = {RSC Advances}, volume = {6}, journal = {RSC Advances}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2046-2069}, doi = {10.1039/c6ra04808k}, pages = {33561 -- 33568}, year = {2016}, abstract = {The aim of this study was to develop a one-step synthesis of gold nanotriangles (NTs) in the presence of mixed phospholipid vesicles followed by a separation process to isolate purified NTs. Negatively charged vesicles containing AOT and phospholipids, in the absence and presence of additional reducing agents (polyampholytes, polyanions or low molecular weight compounds), were used as a template phase to form anisotropic gold nanoparticles. Upon addition of the gold chloride solution, the nucleation process is initiated and both types of particles, i.e., isotropic spherical and anisotropic gold nanotriangles, are formed simultaneously. As it was not possible to produce monodisperse nanotriangles with such a one-step procedure, the anisotropic nanoparticles needed to be separated from the spherical ones. Therefore, a new type of separation procedure using combined polyelectrolyte/micelle depletion flocculation was successfully applied. As a result of the different purification steps, a green colored aqueous dispersion was obtained containing highly purified, well-defined negatively charged flat nanocrystals with a platelet thickness of 10 nm and an edge length of about 175 nm. The NTs produce promising results in surface-enhanced Raman scattering.}, language = {en} } @misc{LiebigSarhanPrietzeletal.2016, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Reinecke, Antje and Koetz, Joachim}, title = {"Green" gold nanotriangles: synthesis, purification by polyelectrolyte/micelle depletion flocculation and performance in surface-enhanced Raman scattering}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-394430}, pages = {33561 -- 33568}, year = {2016}, abstract = {The aim of this study was to develop a one-step synthesis of gold nanotriangles (NTs) in the presence of mixed phospholipid vesicles followed by a separation process to isolate purified NTs. Negatively charged vesicles containing AOT and phospholipids, in the absence and presence of additional reducing agents (polyampholytes, polyanions or low molecular weight compounds), were used as a template phase to form anisotropic gold nanoparticles. Upon addition of the gold chloride solution, the nucleation process is initiated and both types of particles, i.e., isotropic spherical and anisotropic gold nanotriangles, are formed simultaneously. As it was not possible to produce monodisperse nanotriangles with such a one-step procedure, the anisotropic nanoparticles needed to be separated from the spherical ones. Therefore, a new type of separation procedure using combined polyelectrolyte/micelle depletion flocculation was successfully applied. As a result of the different purification steps, a green colored aqueous dispersion was obtained containing highly purified, well-defined negatively charged flat nanocrystals with a platelet thickness of 10 nm and an edge length of about 175 nm. The NTs produce promising results in surface-enhanced Raman scattering.}, language = {en} } @article{SarhanKoopmanSchuetzetal.2019, author = {Sarhan, Radwan Mohamed and Koopman, Wouter-Willem Adriaan and Schuetz, Roman and Schmid, Thomas and Liebig, Ferenc and Koetz, Joachim and Bargheer, Matias}, title = {The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol}, series = {Scientific Reports}, volume = {9}, journal = {Scientific Reports}, publisher = {Macmillan Publishers Limited}, address = {London}, issn = {2045-2322}, doi = {10.1038/s41598-019-38627-2}, pages = {8}, year = {2019}, abstract = {Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding.}, language = {en} } @misc{SarhanKoopmanSchuetzetal.2018, author = {Sarhan, Radwan Mohamed and Koopman, Wouter-Willem Adriaan and Schuetz, Roman and Schmid, Thomas and Liebig, Ferenc and Koetz, Joachim and Bargheer, Matias}, title = {The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol}, series = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, number = {698}, issn = {1866-8372}, doi = {10.25932/publishup-42719}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-427197}, pages = {8}, year = {2018}, abstract = {Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding.}, language = {en} } @article{LiebigHenningSarhanetal.2019, author = {Liebig, Ferenc and Henning, Ricky and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Schmitt, Clemens Nikolaus Zeno and Bargheer, Matias and Koetz, Joachim}, title = {A simple one-step procedure to synthesise gold nanostars in concentrated aqueous surfactant solutions}, series = {RSC Advances}, volume = {9}, journal = {RSC Advances}, publisher = {RSC Publishing}, address = {London}, issn = {2046-2069}, doi = {10.1039/C9RA02384D}, pages = {23633 -- 23641}, year = {2019}, abstract = {Due to the enhanced electromagnetic field at the tips of metal nanoparticles, the spiked structure of gold nanostars (AuNSs) is promising for surface-enhanced Raman scattering (SERS). Therefore, the challenge is the synthesis of well designed particles with sharp tips. The influence of different surfactants, i.e., dioctyl sodium sulfosuccinate (AOT), sodium dodecyl sulfate (SDS), and benzylhexadecyldimethylammonium chloride (BDAC), as well as the combination of surfactant mixtures on the formation of nanostars in the presence of Ag⁺ ions and ascorbic acid was investigated. By varying the amount of BDAC in mixed micelles the core/spike-shell morphology of the resulting AuNSs can be tuned from small cores to large ones with sharp and large spikes. The concomitant red-shift in the absorption toward the NIR region without losing the SERS enhancement enables their use for biological applications and for time-resolved spectroscopic studies of chemical reactions, which require a permanent supply with a fresh and homogeneous solution. HRTEM micrographs and energy-dispersive X-ray (EDX) experiments allow us to verify the mechanism of nanostar formation according to the silver underpotential deposition on the spike surface in combination with micelle adsorption.}, language = {en} } @article{LiebigSarhanSanderetal.2017, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Sander, Mathias and Koopman, Wouter-Willem Adriaan and Schuetz, Roman and Bargheer, Matias and Koetz, Joachim}, title = {Deposition of Gold Nanotriangles in Large Scale Close-Packed Monolayers for X-ray-Based Temperature Calibration and SERS Monitoring of Plasmon-Driven Catalytic Reactions}, series = {ACS applied materials \& interfaces}, volume = {9}, journal = {ACS applied materials \& interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.7b07231}, pages = {20247 -- 20253}, year = {2017}, language = {en} } @article{LiebigSarhanPrietzeletal.2018, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Schmitt, Clemens Nikolaus Zeno and Bargheer, Matias and Koetz, Joachim}, title = {Tuned Surface-Enhanced raman scattering performance of undulated Au@Ag triangles}, series = {ACS applied nano materials}, volume = {1}, journal = {ACS applied nano materials}, number = {4}, publisher = {American Chemical Society}, address = {Washington}, issn = {2574-0970}, doi = {10.1021/acsanm.8b00570}, pages = {1995 -- 2003}, year = {2018}, abstract = {Negatively charged ultraflat gold nanotriangles (AuNTs) stabilized by the anionic surfactant dioctyl sodium sulfosuccinate (AOT) were reloaded with the cationic surfactant benzylhexadecyldimethylammonium chloride (BDAC). Because of the spontaneous formation of a catanionic AOT micelle/BDAC bilayer onto the surface of the reloaded AuNTs, a reduction of Ag+ ions leads to the formation of spherical silver nanoparticles (AgNPs). With increasing concentration of AgNPs on the AuNTs, the localized surface plasmon resonance (LSPR) is shifted stepwise from 1300 to 800 nm. The tunable LSPR enables to shift the extinction maximum to the wavelength of the excitation laser of the Raman microscope at 785 nm. Surface-enhanced Raman scattering (SERS) experiments performed under resonance conditions show an SERS enhancement factor of the analyte molecule rhodamine RG6 of 5.1 X 10(5), which can be related to the silver hot spots at the periphery of the undulated gold nanoplatelets.}, language = {en} } @phdthesis{Sarhan2019, author = {Sarhan, Radwan Mohamed}, title = {Plasmon-driven photocatalytic reactions monitored by surface-enhanced Raman spectroscopy}, doi = {10.25932/publishup-43330}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-433304}, school = {Universit{\"a}t Potsdam}, year = {2019}, abstract = {Plasmonic metal nanostructures can be tuned to efficiently interact with light, converting the photons into energetic charge carriers and heat. Therefore, the plasmonic nanoparticles such as gold and silver nanoparticles act as nano-reactors, where the molecules attached to their surfaces benefit from the enhanced electromagnetic field along with the generated energetic charge carriers and heat for possible chemical transformations. Hence, plasmonic chemistry presents metal nanoparticles as a unique playground for chemical reactions on the nanoscale remotely controlled by light. However, defining the elementary concepts behind these reactions represents the main challenge for understanding their mechanism in the context of the plasmonically assisted chemistry. Surface-enhanced Raman scattering (SERS) is a powerful technique employing the plasmon-enhanced electromagnetic field, which can be used for probing the vibrational modes of molecules adsorbed on plasmonic nanoparticles. In this cumulative dissertation, I use SERS to probe the dimerization reaction of 4-nitrothiophenol (4-NTP) as a model example of plasmonic chemistry. I first demonstrate that plasmonic nanostructures such as gold nanotriangles and nanoflowers have a high SERS efficiency, as evidenced by probing the vibrations of the rhodamine dye R6G and the 4-nitrothiophenol 4-NTP. The high signal enhancement enabled the measurements of SERS spectra with a short acquisition time, which allows monitoring the kinetics of chemical reactions in real time. To get insight into the reaction mechanism, several time-dependent SERS measurements of the 4-NTP have been performed under different laser and temperature conditions. Analysis of the results within a mechanistic framework has shown that the plasmonic heating significantly enhances the reaction rate, while the reaction is probably initiated by the energetic electrons. The reaction was shown to be intensity-dependent, where a certain light intensity is required to drive the reaction. Finally, first attempts to scale up the plasmonic catalysis have been performed showing the necessity to achieve the reaction threshold intensity. Meanwhile, the induced heat needs to quickly dissipate from the reaction substrate, since otherwise the reactants and the reaction platform melt. This study might open the way for further work seeking the possibilities to quickly dissipate the plasmonic heat generated during the reaction and therefore, scaling up the plasmonic catalysis.}, language = {en} } @article{LiebigSarhanSchmittetal.2020, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Schmitt, Clemens Nikolaus Zeno and Th{\"u}nemann, Andreas F. and Prietzel, Claudia Christina and Bargheer, Matias and Koetz, Joachim}, title = {Gold nanotriangles with crumble topping and their influence on catalysis and surface-enhanced raman spectroscopy}, series = {ChemPlusChem}, volume = {85}, journal = {ChemPlusChem}, number = {3}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2192-6506}, doi = {10.1002/cplu.201900745}, pages = {519 -- 526}, year = {2020}, abstract = {By adding hyaluronic acid (HA) to dioctyl sodium sulfosuccinate (AOT)-stabilized gold nanotriangles (AuNTs) with an average thickness of 7.5 +/- 1 nm and an edge length of about 175 +/- 17 nm, the AOT bilayer is replaced by a polymeric HA-layer leading to biocompatible nanoplatelets. The subsequent reduction process of tetrachloroauric acid in the HA-shell surrounding the AuNTs leads to the formation of spherical gold nanoparticles on the platelet surface. With increasing tetrachloroauric acid concentration, the decoration with gold nanoparticles can be tuned. SAXS measurements reveal an increase of the platelet thickness up to around 14.5 nm, twice the initial value of bare AuNTs. HRTEM micrographs show welding phenomena between densely packed particles on the platelet surface, leading to a crumble formation while preserving the original crystal structure. Crumbles crystallized on top of the platelets enhance the Raman signal by a factor of around 20, and intensify the plasmon-driven dimerization of 4-nitrothiophenol (4-NTP) to 4,4 '-dimercaptoazobenzene in a yield of up to 50 \%. The resulting crumbled nanotriangles, with a biopolymer shell and the absorption maximum in the second window for in vivo imaging, are promising candidates for biomedical sensing.}, language = {en} } @article{ZhaoSarhanEljarratetal.2022, author = {Zhao, Yuhang and Sarhan, Radwan Mohamed and Eljarrat, Alberto and Kochovski, Zdravko and Koch, Christoph and Schmidt, Bernd and Koopman, Wouter-Willem Adriaan and Lu, Yan}, title = {Surface-functionalized Au-Pd nanorods with enhanced photothermal conversion and catalytic performance}, series = {ACS applied materials \& interfaces}, volume = {14}, journal = {ACS applied materials \& interfaces}, number = {15}, publisher = {American Chemical Society}, address = {Washington, DC}, issn = {1944-8244}, doi = {10.1021/acsami.2c00221}, pages = {17259 -- 17272}, year = {2022}, abstract = {Bimetallic nanostructures comprising plasmonic and catalytic components have recently emerged as a promising approach to generate a new type of photo-enhanced nanoreactors. Most designs however concentrate on plasmon-induced charge separation, leaving photo-generated heat as a side product. This work presents a photoreactor based on Au-Pd nanorods with an optimized photothermal conversion, which aims to effectively utilize the photo-generated heat to increase the rate of Pd-catalyzed reactions. Dumbbell-shaped Au nanorods were fabricated via a seed-mediated growth method using binary surfactants. Pd clusters were selectively grown at the tips of the Au nanorods, using the zeta potential as a new synthetic parameter to indicate the surfactant remaining on the nanorod surface. The photothermal conversion of the Au-Pd nanorods was improved with a thin layer of polydopamine (PDA) or TiO2. As a result, a 60\% higher temperature increment of the dispersion compared to that for bare Au rods at the same light intensity and particle density could be achieved. The catalytic performance of the coated particles was then tested using the reduction of 4-nitrophenol as the model reaction. Under light, the PDA-coated Au-Pd nanorods exhibited an improved catalytic activity, increasing the reaction rate by a factor 3. An analysis of the activation energy confirmed the photoheating effect to be the dominant mechanism accelerating the reaction. Thus, the increased photothermal heating is responsible for the reaction acceleration. Interestingly, the same analysis shows a roughly 10\% higher reaction rate for particles under illumination compared to under dark heating, possibly implying a crucial role of localized heat gradients at the particle surface. Finally, the coating thickness was identified as an essential parameter determining the photothermal conversion efficiency and the reaction acceleration.}, language = {en} } @article{PanSarhanKochovskietal.2022, author = {Pan, Xuefeng and Sarhan, Radwan Mohamed and Kochovski, Zdravko and Chen, Guosong and Taubert, Andreas and Mei, Shilin and Lu, Yan}, title = {Template synthesis of dual-functional porous MoS2 nanoparticles with photothermal conversion and catalytic properties}, series = {Nanoscale}, volume = {14}, journal = {Nanoscale}, number = {18}, publisher = {RSC Publ. (Royal Society of Chemistry)}, address = {Cambridge}, issn = {2040-3372}, doi = {10.1039/d2nr01040b}, pages = {6888 -- 6901}, year = {2022}, abstract = {Advanced catalysis triggered by photothermal conversion effects has aroused increasing interest due to its huge potential in environmental purification. In this work, we developed a novel approach to the fast degradation of 4-nitrophenol (4-Nip) using porous MoS2 nanoparticles as catalysts, which integrate the intrinsic catalytic property of MoS2 with its photothermal conversion capability. Using assembled polystyrene-b-poly(2-vinylpyridine) block copolymers as soft templates, various MoS 2 particles were prepared, which exhibited tailored morphologies (e.g., pomegranate-like, hollow, and open porous structures). The photothermal conversion performance of these featured particles was compared under near-infrared (NIR) light irradiation. Intriguingly, when these porous MoS2 particles were further employed as catalysts for the reduction of 4-Nip, the reaction rate constant was increased by a factor of 1.5 under NIR illumination. We attribute this catalytic enhancement to the open porous architecture and light-to-heat conversion performance of the MoS2 particles. This contribution offers new opportunities for efficient photothermal-assisted catalysis.}, language = {en} }