Bu çalışma Helsinki Üniversitesi ve Jane ve Aatos Erkko Vakfı tarafından desteklendi. S.H. burs için Erasmus+ AB fonlarına teşekkür ediyor.

1. Ag-Pd/ZrO2 NPs Sentezi 
NOT: Bu prosedürde, Ag-Pd'deki Pd mol% 1'e ve ZrO2'deki Ag-Pd yüklemesi 3 wt.% 'ye karşılık geldi.
<ol><li>250 mL'lik bir kabın içine1 g ZrO 2 tozu yerleştirin.</li>
	<li>Oda sıcaklığında güçlü manyetik karıştırma (500 rpm) altında behere 50 mL AgNO3 (aq)(0,0059mol/L) ve 9,71 mL K 2 PdCl4 (aq) (0,00031 mol/L) çözeltisi ekleyin.</li>
	<li>10 mL lizin (0,53 M) sulu çözelti ekleyin.</li>
	<li>Karışımı 20 dakika boyunca kuvvetli karıştırma (500 rpm) altında tutun.</li>
	<li>20 dakika sonra, süspansiyona yeni hazırlanmış bir NaBH 4 (aq)(0.035 M) çözeltisinin 10 mL'lik süspansiyonu damla yönünde, 1 mL / dak hızında eklemek için bir pipet kullanın. Süspansiyonu işlem boyunca karıştırma (500 rpm) altında tutun.</li>
	<li>Karışımı oda sıcaklığında 30 dakika karıştırın.</li>
</ol>2. Katalizörün ayrılması ve saflaştırılması
<ol><li>Süspansiyonu santrifüj tüplerine aktarın ve katıları 10 dakika boyunca 3.260 x g'da santrifüjleme ile karışımdan ayırın.</li>
	<li>Sıvı fazı bir pipetle dikkatlice çıkarın ve tüplere 15 mL deiyonize su ekleyin.<ol>
<li>Katının dağılımı elde edilene kadar kuvvetlice çalkalayın. İyi dağılım sağlanamazsa, tüpleri 5 dakika boyunca ultrasonik bir banyoya yerleştirin.</li>
		<li>Dispersiyon 10 dakika boyunca 3.260 x g'da santrifüj.</li>
	</ol>
</li>
	<li>Yıkama adımlarını (2.2. ila 2.2.2.) iki kez daha iyonize su kullanarak, ardından su yerine etanol kullanarak tekrarlayın.</li>
	<li>Etanolleri çıkarın ve katıyı 60 °C'de bir fırında 12 saat kurutun.</li>
	<li>Hazırlanan Ag-Pd/ZrO2 NP'leri çeşitli mikroskopi, elementel ve spektroskopik tekniklerle karakterize edin.</li>
</ol>3. Ag/ZrO2 NPs Sentezi 
NOT: Bu prosedürde, ZrO2'ye Ag yüklemesi 3 wt.% 'ye karşılık gelir.
<ol><li>250 mL'lik bir kabın içine1 g ZrO 2 tozu yerleştirin.</li>
	<li>Oda sıcaklığında kuvvetli manyetik karıştırma (500 rpm) altında behere 50 mL AgNO3 (aq) (0.0059 mol/L) çözeltisi ekleyin.</li>
	<li>10 mL lizin (0,53 M) sulu çözelti ekleyin.</li>
	<li>Karışımı 20 dakika boyunca kuvvetli karıştırma (500 rpm) altında tutun.</li>
	<li>20 dakika sonra, süspansiyona yeni hazırlanmış bir NaBH 4 (aq)(0.035 M) çözeltisinin 10 mL'lik süspansiyonu damla yönünde, 1 mL / dak hızında eklemek için bir pipet kullanın. Süspansiyonu işlem boyunca karıştırma (500 rpm) altında tutun.</li>
	<li>Karışımı oda sıcaklığında 30 dakika karıştırın.</li>
</ol>4. Katalizörün ayrılması ve saflaştırılması
<ol><li>Süspansiyonu santrifüj tüplerine aktarın ve katıları 10 dakika boyunca 3.260 x g'da santrifüjleme ile karışımdan ayırın.</li>
	<li>Sıvı fazı bir pipetle dikkatlice çıkarın ve tüplere 15 mL deiyonize su ekleyin.<ol>
<li>Katının dağılımı gözlenene kadar kuvvetlice çalkalayın. İyi dağılım sağlanamazsa, tüpleri 5 dakika boyunca ultrasonik bir banyoya yerleştirin.</li>
		<li>Dispersiyon 10 dakika boyunca 3.260 x g'da santrifüj.</li>
	</ol>
</li>
	<li>Yıkama adımlarını (4.2. ila 4.2.2.) iki kez daha iyonize su kullanarak, ardından su yerine etanol kullanarak tekrarlayın.</li>
	<li>Etanolleri çıkarın ve katıyı 60 °C'de bir fırında 12 saat kurutun.</li>
	<li>Hazırlanan Ag/ZrO2 NP'ler daha sonra çeşitli mikroskopi, elementel ve spektroskopik tekniklerle karakterize edilebilir.</li>
</ol>5. LSPR uyarımı (ışık aydınlatması) altında nitrobenzen azaltma yönünde plazmonik katalitik performansın araştırılması
<ol><li>Manyetik karıştırma çubuğu ile birlikte 25 mL yuvarlak tabanlı bir şişeye 30 mg katalizör yerleştirin.</li>
	<li>Reaktöre izopropil alkolde (IPA) 5 mL nitrobenzen çözeltisi (0,03 mol/L) ekleyin.</li>
	<li>Ardından, 11.22 mg KOH tozu (0.0002 mol) ekleyin.</li>
	<li>Süspansiyonu 1 dakika boyunca argon akışı ile köpürterek reaktörü arındırın. Temizledikten hemen sonra şişeyi kapatın.</li>
	<li>Reaktörü sıcaklık kontrollü manyetik karıştırıcının (500 rpm) üzerinde 70 °C'de ısıtılmış bir yağ banyosuna yerleştirin.</li>
	<li>Işık kaynağı olarak dalga boyu 425 nm olan 4 LED lamba ve 0,5 W/cm2ışık yoğunluğu ile tüpü ışınlayın. Lambalardan reaksiyon şişesine olan mesafe 7 cm olmalıdır.</li>
	<li>Reaksiyonun kuvvetli manyetik karıştırma (500 rpm) altında 70 °C'de 2,5 saat devam etmesine izin verin.</li>
	<li>Ardından, ışığı kapatın, reaktörü açın ve 1 mL'lik bir örnek toplamak için bir şırınga ve bir iğne kullanın. Katalizör partiküllerini çıkarmak için 0,45 μm filtreden geçirerek bir gaz kromatografi şişesine filtreleyin.</li>
</ol>6. LSPR ekscitasyonunun yokluğunda reaksiyon (karanlık koşullar)
<ol><li>5'te açıklanan adımları izleyin, ancak ışık ışınlama olmadan. Işığa maruz kalmayı önlemek için reaksiyon tüpünü alüminyum folyo ile sarın.</li>
</ol>7. Gaz kromatografisi (GC) analiz hazırlığı
<ol><li>Yaklaşık 30 mmol/L nitrobenzen (NB), 30 mmol/L anilin (AN) ve 30 mmol/L azobenzen (AB) içeren bir IPA çözeltisi hazırlayın.</li>
	<li>Uygun bir yöntem kullanarak çözümün GC analizini çalıştırın. Kolon sıcaklığı ve gaz akış programları değiştirilerek farklı yöntemler test edilebilir. Seçilen yöntem, IPA, NB, AN ve AB'ye karşılık gelen tepeleri minimum saklama süresi içinde ayırabilmelidir.</li>
	<li>Yöntem seçildikten sonra, IPA'da 50 mM, 25 mM, 10 mM, 5 mM ve 2,5 mM NB'lik bir çözüm seti ve aynı konsantrasyonlarda IPA'da başka bir AN ve AB çözümleri seti hazırlayın.</li>
	<li>Hazırlanan çözümlerin GC analizini çalıştırın. Her kromatogram 2 tepe noktası sunmalıdır: daha yüksek olan IPA'ya ve daha düşük olanı NB, AN veya AB'ye karşılık gelir. Her kromatogram için, tüm tepelerin tutma süresini ve tepe alanını not edin.</li>
	<li>Her numunenin yoğun alanına karşı konsantrasyonu çizerek NB, AN ve AB kalibrasyon eğrilerini takip edin.</li>
</ol>8. GC analizi
<ol><li>5. adımlarda toplanan örnekler üzerinde bir GC analizi çalıştırın. ve 6. 7.2 adımları için kullanılan yöntemle. ve 7.4.</li>
	<li>Her kromatogram için saklama süresini ve tepe alanını not edin ve numunelerdeki NB, AN ve AB konsantrasyonunu belirlemek için daha önce çizilen kalibrasyon eğrilerini kullanın.</li>
	<li>Denklemleri kullanarak nitrobenzen dönüşümünün yanı sıra anilin ve azobenzen seçiciliğini hesaplayın: <img alt="Equation 1" src="/files/ftp_upload/61712/61712eq1.jpg"> <img alt="Equation 2" src="/files/ftp_upload/61712/61712eq2.jpg"> <img alt="Equation 3" src="/files/ftp_upload/61712/61712eq3.jpg"> <img alt="Equation 4" src="/files/ftp_upload/61712/61712eq4.jpg">GC analizinin 2,5 saatlik reaksiyonu sonrasında ilk NBkonsantrasyonu (0,03 mol/L) ve C NB , C AN , C AB sırasıyla NB, AN ve AB konsantrasyonlarına karşılık gelir.</li>
</ol>

<ol>
	<li>Dunn, P. J., Hii, K. K., Krische, M. J., Williams, M. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Sustainable Catalysis: Challenges and Pratices for the Pharmaceutical and Fine Chemical Industries. , (2013).</li><li>Tzouras, N. V., Stamatopoulos, I. K., Papastavrou, A. T., Liori, A. A., Vougioukalakis, G. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sustainable+metal+catalysis+in+C-H+activation.">Sustainable metal catalysis in C-H activation.</a> Coordination Chemistry Reviews. 343, 25 (2017).</li><li>Polshettiwar, V., Varma, R. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Green+chemistry+by+nano-catalysis.">Green chemistry by nano-catalysis.</a> Green Chemistry. 12 (5), 743 (2010).</li><li>Rodrigues, T. S., da Silva, A. G. M., Camargo, P. H. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanocatalysis+by+noble+metal+nanoparticles:+controlled+synthesis+for+the+optimization+and+understanding+of+activities.">Nanocatalysis by noble metal nanoparticles: controlled synthesis for the optimization and understanding of activities.</a> Journal of Materials Chemistry A. 7 (11), 5857-5874 (2019).</li><li>Linic, S., Christopher, P., Ingram, D. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmonic-metal+nanostructures+for+efficient+conversion+of+solar+to+chemical+energy.">Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy.</a> Nature Materials. 10 (12), 911-921 (2011).</li><li>Nam, J. M., Liz-Marz&#225;n, L., Halas, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chemical+Nanoplasmonics:+Emerging+Interdisciplinary+Research+Field+at+Crossroads+between+Nanoscale+Chemistry+and+Plasmonics.">Chemical Nanoplasmonics: Emerging Interdisciplinary Research Field at Crossroads between Nanoscale Chemistry and Plasmonics.</a> Accounts of Chemical Research. 52 (11), 2995-2996 (2019).</li><li>Brongersma, M. L., Halas, N. J., Nordlander, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmon-induced+hot+carrier+science+and+technology.">Plasmon-induced hot carrier science and technology.</a> Nature Nanotechnology. 10 (1), 25-34 (2015).</li><li>Smith, J. G., Faucheaux, J. A., Jain, P. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmon+resonances+for+solar+energy+harvesting:+A+mechanistic+outlook.">Plasmon resonances for solar energy harvesting: A mechanistic outlook.</a> Nano Today. 10 (1), 67-80 (2015).</li><li>Hartland, G. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Optical+studies+of+dynamics+in+noble+metal+nanostructures.">Optical studies of dynamics in noble metal nanostructures.</a> Chemical Reviews. 111 (6), 3858-3887 (2011).</li><li>Kelly, K. L., Coronado, E., Zhao, L. L., Schatz, G. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+optical+properties+of+metal+nanoparticles:+The+influence+of+size,+shape,+and+dielectric+environment.">The optical properties of metal nanoparticles: The influence of size, shape, and dielectric environment.</a> Journal of Physical Chemistry B. 107 (3), 668-677 (2003).</li><li>Hermoso, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Triangular+metal+nanoprisms+of+Ag,+Au,+and+Cu:+Modeling+the+influence+of+size,+composition,+and+excitation+wavelength+on+the+optical+properties.">Triangular metal nanoprisms of Ag, Au, and Cu: Modeling the influence of size, composition, and excitation wavelength on the optical properties.</a> Chemical Physics. 423, 142-150 (2013).</li><li>Kumar, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rational+Design+and+Development+of+Lanthanide-Doped+NaYF4@CdS-Au-RGO+as+Quaternary+Plasmonic+Photocatalysts+for+Harnessing+Visible-Near-Infrared+Broadband+Spectrum.">Rational Design and Development of Lanthanide-Doped NaYF4@CdS-Au-RGO as Quaternary Plasmonic Photocatalysts for Harnessing Visible-Near-Infrared Broadband Spectrum.</a> ACS Applied Materials and Interfaces. 10 (18), 15565-15581 (2018).</li><li>Reddy, K. L., Kumar, S., Kumar, A., Krishnan, V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Wide+spectrum+photocatalytic+activity+in+lanthanide-doped+upconversion+nanophosphors+coated+with+porous+TiO2+and+Ag-Cu+bimetallic+nanoparticles.">Wide spectrum photocatalytic activity in lanthanide-doped upconversion nanophosphors coated with porous TiO2 and Ag-Cu bimetallic nanoparticles.</a> Journal of Hazardous Materials. 367, 694-705 (2019).</li><li>Ingram, D. B., Linic, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Water+splitting+on+composite+plasmonic-metal/semiconductor+photoelectrodes:+Evidence+for+selective+plasmon-induced+formation+of+charge+carriers+near+the+semiconductor+surface.">Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: Evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface.</a> Journal of the American Chemical Society. 133 (14), 5202-5205 (2011).</li><li>Linic, S., Aslam, U., Boerigter, C., Morabito, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photochemical+transformations+on+plasmonic+metal+nanoparticles.">Photochemical transformations on plasmonic metal nanoparticles.</a> Nature Materials. 14 (6), 567-576 (2015).</li><li>Aslam, U., Rao, V. G., Chavez, S., Linic, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalytic+conversion+of+solar+to+chemical+energy+on+plasmonic+metal+nanostructures.">Catalytic conversion of solar to chemical energy on plasmonic metal nanostructures.</a> Nature Catalyst. 1, 656-665 (2018).</li><li>Araujo, T. P., Quiroz, J., Barbosa, E. C. M., Camargo, P. H. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Understanding+plasmonic+catalysis+with+controlled+nanomaterials+based+on+catalytic+and+plasmonic+metals.">Understanding plasmonic catalysis with controlled nanomaterials based on catalytic and plasmonic metals.</a> Current Opinion in Colloid and Interface Science. 39, 110-122 (2019).</li><li>Gell&#233;, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Applications+of+plasmon-enhanced+nanocatalysis+to+organic+transformations.">Applications of plasmon-enhanced nanocatalysis to organic transformations.</a> Chemical Reviews. , 986-1041 (2020).</li><li>Shaik, F., Peer, I., Jain, P. K., Amirav, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmon-Enhanced+Multicarrier+Photocatalysis.">Plasmon-Enhanced Multicarrier Photocatalysis.</a> Nano Letters. 18 (7), 4370-4376 (2018).</li><li>Quiroz, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlling+Reaction+Selectivity+over+Hybrid+Plasmonic+Nanocatalysts.">Controlling Reaction Selectivity over Hybrid Plasmonic Nanocatalysts.</a> Nano Letters. 18, 7289-7297 (2018).</li><li>Peiris, E., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmonic+Switching+of+the+Reaction+Pathway:+Visible-Light+Irradiation+Varies+the+Reactant+Concentration+at+the+Solid-Solution+Interface+of+a+Gold-Cobalt+Catalyst.">Plasmonic Switching of the Reaction Pathway: Visible-Light Irradiation Varies the Reactant Concentration at the Solid-Solution Interface of a Gold-Cobalt Catalyst.</a> Angewandte Chemie - International Edition. 58 (35), 12032-12036 (2019).</li><li>Yu, S., Wilson, A. J., Heo, J., Jain, P. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmonic+Control+of+Multi-Electron+Transfer+and+C-C+Coupling+in+Visible-Light-Driven+CO2+Reduction+on+Au+Nanoparticles.">Plasmonic Control of Multi-Electron Transfer and C-C Coupling in Visible-Light-Driven CO2 Reduction on Au Nanoparticles.</a> Nano Letters. 18 (4), 2189-2194 (2018).</li><li>Yu, S., Jain, P. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmonic+photosynthesis+of+C+1+-C+3+hydrocarbons+from+carbon+dioxide+assisted+by+an+ionic+liquid.">Plasmonic photosynthesis of C 1 -C 3 hydrocarbons from carbon dioxide assisted by an ionic liquid.</a> Nature Communications. 10, 2022 (2019).</li><li>Zhang, X., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Product+selectivity+in+plasmonic+photocatalysis+for+carbon+dioxide+hydrogenation.">Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation.</a> Nature Communications. 8, 1-9 (2017).</li><li>Cort&#233;s, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficiency+and+Bond+Selectivity+in+Plasmon-Induced+Photochemistry.">Efficiency and Bond Selectivity in Plasmon-Induced Photochemistry.</a> Advanced Optical Materials. 5 (15), 1700191 (2017).</li><li>de Freitas, I. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Design-controlled+synthesis+of+IrO+2+sub-monolayers+on+Au+nanoflowers:+marrying+plasmonic+and+electrocatalytic+properties.">Design-controlled synthesis of IrO 2 sub-monolayers on Au nanoflowers: marrying plasmonic and electrocatalytic properties.</a> Nanoscale. , 23-27 (2020).</li><li>Zhang, C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Al-Pd+Nanodisk+Heterodimers+as+Antenna-Reactor+Photocatalysts.">Al-Pd Nanodisk Heterodimers as Antenna-Reactor Photocatalysts.</a> Nano Letters. 16 (10), 6677-6682 (2016).</li><li>Zhou, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Light-driven+methane+dry+reforming+with+single+atomic+site+antenna-reactor+plasmonic+photocatalysts.">Light-driven methane dry reforming with single atomic site antenna-reactor plasmonic photocatalysts.</a> Nature Energy. 5, 61-70 (2020).</li><li>Swearer, D. F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Heterometallic+antenna-reactor+complexes+for+photocatalysis.">Heterometallic antenna-reactor complexes for photocatalysis.</a> Proceedings of the National Academy of Sciences. 113 (32), 8916-8920 (2016).</li><li>Peiris, S., Sarina, S., Han, C., Xiao, Q., Zhu, H. -. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Silver+and+palladium+alloy+nanoparticle+catalysts:+reductive+coupling+of+nitrobenzene+through+light+irradiation.">Silver and palladium alloy nanoparticle catalysts: reductive coupling of nitrobenzene through light irradiation.</a> Dalton Transactions. 46 (32), 10665-10672 (2017).</li><li>Rahm, J. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Library+of+Late+Transition+Metal+Alloy+Dielectric+Functions+for+Nanophotonic+Applications.">A Library of Late Transition Metal Alloy Dielectric Functions for Nanophotonic Applications.</a> Advanced Functional Materials. 2002122, 02122 (2020).</li><li>Zhang, C., Chen, B. Q., Li, Z. Y., Xia, Y., Chen, Y. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+Plasmon+Resonance+in+Bimetallic+Core-Shell+Nanoparticles.">Surface Plasmon Resonance in Bimetallic Core-Shell Nanoparticles.</a> Journal of Physical Chemistry C. 119 (29), 16836-16845 (2015).</li><li>Liu, Z., Huang, Y., Xiao, Q., Zhu, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+reduction+of+nitroaromatics+to+azoxy+compounds+on+supported+Ag-Cu+alloy+nanoparticles+through+visible+light+irradiation.">Selective reduction of nitroaromatics to azoxy compounds on supported Ag-Cu alloy nanoparticles through visible light irradiation.</a> Green Chemistry. 18 (3), 817-825 (2016).</li><li>Chaiseeda, K., Nishimura, S., Ebitani, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Gold+nanoparticles+supported+on+alumina+as+a+catalyst+for+surface+plasmon-enhanced+selective+reductions+of+nitrobenzene.">Gold nanoparticles supported on alumina as a catalyst for surface plasmon-enhanced selective reductions of nitrobenzene.</a> ACS Omega. 2 (10), 7066-7070 (2017).</li><li>Peiris, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal+nanoparticle+photocatalysts:+emerging+processes+for+green+organic+synthesis.">Metal nanoparticle photocatalysts: emerging processes for green organic synthesis.</a> Catalysis Science and Technology. 6 (2), 320-338 (2016).</li><li>Garc&#237;a-Garc&#237;a, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Silver-Based+Plasmonic+Catalysts+for+Carbon+Dioxide+Reduction.">Silver-Based Plasmonic Catalysts for Carbon Dioxide Reduction.</a> ACS Sustainable Chemistry and Engineering. 8 (4), 1879-1887 (2020).</li><li>Agrawal, A., Johns, R. W., Milliron, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Control+of+Localized+Surface+Plasmon+Resonances+in+Metal+Oxide+Nanocrystals.">Control of Localized Surface Plasmon Resonances in Metal Oxide Nanocrystals.</a> Annual Review of Materials Research. 47 (1), 1-31 (2017).</li><li>Lounis, S. D., Runnerstrom, E. L., Llord&#233;s, A., Milliron, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Defect+chemistry+and+Plasmon+physics+of+colloidal+metal+oxide+Nanocrystals.">Defect chemistry and Plasmon physics of colloidal metal oxide Nanocrystals.</a> Journal of Physical Chemistry Letters. 5 (9), 1564-1574 (2014).</li><li>Rej, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determining+Plasmonic+Hot+Electrons+and+Photothermal+Effects+during+H2+Evolution+with+TiN-Pt+Nanohybrids.">Determining Plasmonic Hot Electrons and Photothermal Effects during H2 Evolution with TiN-Pt Nanohybrids.</a> ACS Catalysis. 10 (9), 5261-5271 (2020).</li><li>Barragan, A. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photochemistry+of+Plasmonic+Titanium+Nitride+Nanocrystals.">Photochemistry of Plasmonic Titanium Nitride Nanocrystals.</a> The Journal of Physical Chemistry C. 123 (35), 21796-21804 (2019).</li></ol>

Yazarların açıklayacak bir şeyi yok.

Bu yöntemde açıklanan bulgular, Pd'nin (veya diğer katalitik ancak plazmonik metalin değil) içsel katalitik aktivitesinin, bimetalik alaşımlıNPs 35'tegörünür ışık ışınlama yoluyla LSPR ekscitasyonu ile önemli ölçüde artırılabileceğini göstermektedir. Bu durumda, Ag (veya başka bir plazmonik metal), LSPR ekscitasyonu yoluyla görünür ışık ışınlamasından enerji toplama yeteneğine sahiptir. LSPR eksitasyonu, sıcak yük taşıyıcılarının (sıcak elektronlar ve...

Metal nanopartiküllerin (NPs) çeşitli uygulamaları arasında, kataliz özel ilgiyi hak eder. Kataliz, sürdürülebilir bir gelecekte merkezi bir rol oynar, daha az enerji tüketimine, hammaddelerin daha iyi kullanılmasına katkıda bulunan ve daha temiz reaksiyon koşulları sağlayan1,2,3,4. Bu nedenle, katalizdeki ilerleme, kimyasal proseslerin atomik verimliliğini artırmak için araçlar sağlayabilir, bu da onları daha temiz, ekonomik olarak daha uygulanabilir ve daha çevre dostu hale getirebilir. Gümüş (Ag), altın (Au) veya bakırı (Cu) kapsayan metal NP'ler, bu sistemlerin yerelleştirilmiş yüzey plazmon rezonansı (LSPR) eksize etme 5 ,6,7,8aracılığıyla nano ölçekte ışıkla etkileşime girmelerinin benzersiz yolundan kaynaklanan görünür aralıkta ilginç optik özellikler görüntüleyebilir. Plazmonik NP'ler olarak adlandırılan bu NP'lerde LSPR, 5 ,6,7,8elektronlarının kolektif hareketiyle olay fotonları (gelen bir elektromanyetik dalgadan) arasındaki rezonans etkileşimini içerir. Bu fenomen, ortamın büyüklüğüne, şekline, bileşimine ve dielektrik sabitine bağlı karakteristik bir frekansta gerçekleşir9,10,11. Örneğin, Ag, Au ve Cu için, bu frekanslar görünürden yakın IR'ye kadar değişebilir ve LSPR 5 , 6 ,7,8,12,13'üheyecanlandırmak için güneş enerjisinin kullanımı için olanaklar açabilir.
Son zamanlarda, plazmonik NP'lerdeki LSPR ekscitasyonunun oranları hızlandırmaya ve moleküler dönüşümlerin seçiciliğini kontrol etmeye katkıda bulunabileceği gösterilmiştir5,14,15,16,17,18,19. Bu, kimyasal dönüşümleri hızlandırmak, sürmek ve / veya kontrol etmek için ışıktan enerji kullanmaya odaklanan plazmonik kataliz adı verilen bir alan doğurdu5,14,15,16,17,18,19. Bu bağlamda, plazmonik NP'lerdeki LSPR ekscitasyonunun, LSPR heyecanlı sıcak taşıyıcılar olarak adlandırılan enerjik sıcak elektronların ve deliklerin oluşumuna yol açabileceği tespit edilmiştir. Bu taşıyıcılar elektronik veya titreşimsel aktivasyon yoluyla adsorbe türlerle etkileşime girebilir15,16. Artan reaksiyon oranlarına ek olarak, bu işlem ayrıca geleneksel termokimyasal tahrikli süreçler aracılığıyla erişilemeyen alternatif reaksiyon yolları sağlayabilir ve reaksiyon seçiciliği üzerinde kontrol için yeni yollar açabilir20,21,22,23,24,25. Daha da önemlisi, plazmon çürümesinin termal dağmaya da yol açabileceğini ve NP'lerin çevresinde sıcaklık artışına yol açabileceğini ve reaksiyon oranlarını hızlandırmaya da katkıda bulunabileceğini belirtmek gerekir15,16.
Bu ilginç özellikler nedeniyle, plazmonik kataliz çeşitli moleküler dönüşümlere doğru başarıyla18. Bununla birlikte, önemli bir zorluk devam ediyor. Ag ve Au gibi plazmonik NP'ler görünür ve IR'ye yakın aralıklarda mükemmel optik özellikler gösterirken, katalitik özellikleri dönüşümlerin kapsamı açısından sınırlıdır. Başka bir deyişle, birkaç dönüşüm için iyi katalitik özellikler göstermezler. Ayrıca, paladyum (Pd) ve platin (Pt) gibi katalizörde önemli olan metaller, görünür veya IR'ye yakın aralıklarda LSPR ekscitasyonunu desteklemez. Bu boşluğu kapatmak için, plazmonik ve katalitik metal içeren bimetalik NP'ler etkili bir stratejiyi temsil eder20,26,27,28,29. Bu sistemlerde, plazmonik metal, daha sonra katalitik metaldeki moleküler dönüşümleri sürmek, hızlandırmak ve kontrol etmek için kullanılan LSPR aracılığıyla ışık ekscitasyonundan enerji toplamak için bir anten olarak kullanılabilir. Bu nedenle, bu strateji plazmonik katalizini geleneksel plazmonik metalNPs 20 , 26,27,28,29'un ötesine uzatmamızı sağlar.
Bu protokol, plazyonik kataliz için plazmonik katalitik bir sistem görevi görebilen ZrO2'de (Ag-Pd/ZrO2)desteklenen bimetalik gümüş-paladyum (Ag-Pd) alaşımlı NP'lerin fasile sentezini açıklar. Ag-Pd/ZrO2 NP'ler, ZrO2 desteğindeki ilgili metal öncüllerinin eşzamanlı olarak emprenye edilmesi ve ardından eşzamanlı azaltma30ile hazırlanmıştır. Bu yaklaşım, ZrO 2 desteğinin yüzeyinde yaklaşık 10 nm büyüklüğünde (çap) bimetalikNP'lerin oluşmasına yol açtı. NP'ler, ortaya çıkan Ag-Pd NP'lerin optik özelliklerini en üst düzeye çıkarırken katalitik metalin kullanımını en aza indirmek için Pd'nin% 1'inden oluşuyordu. Nitrobenzenin azaltılması için plazmonik katalizde Ag-Pd/ZrO2 NPs uygulamasına ilişkin bir protokol gösterilmiştir. LSPR excitation için 425 nm LED aydınlatma istihdam ettik. Karanlık ve açık ışınlama koşullarında azalma reaksiyonunun dönüşümünü ve seçiciliğini izlemek için gaz kromatografisi yapıldı. LSPR ekscitasyonu, Ag-Pd/ZrO2 NP'lerde tamamen termal tahrikli koşullara göre katalitik performansın artmasına ve seçicilik üzerinde kontrole yol açtı. Bu protokolde açıklanan yöntem, gaz kromatografisi ile birleştirilmiş basit bir fotokatalitik reaksiyon kurulumuna dayanmaktadır ve çok çeşitli moleküler dönüşümlere ve NP kompozisyonlarına uyarlanabilir. Bu nedenle, bu yöntem fotokatalitik aktivitenin, dönüşüm ve reaksiyon seçiciliği açısından, farklı NP'lerin ve sayısız sıvı fazlı dönüşüm için karakterizeini mümkün kılar. Bu makalenin hem yeni gelenlere hem de alanında daha deneyimli bilim insanlarına önemli yönergeler ve içgörüler sağlayacağına inanıyoruz.

<table border="0" cellpadding="0" cellspacing="0" style="width:727px;" width="726">
	<colgroup>
		<col />
		<col />
		<col />
		<col />
	</colgroup>
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">2-Propanol (anhydrous, 99.5%)</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">278475</td>
			<td style="width:89px;">CAS Number 67-63-0</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Aniline (for synthesis)</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">8.22256</td>
			<td style="width:89px;">CAS Number 62-53-3</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Azobenzene (98%)</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">424633</td>
			<td style="width:89px;">CAS Number 103-33-3</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Ethanol</td>
			<td style="width:96px;">Honeywell</td>
			<td style="width:114px;">32221</td>
			<td style="width:89px;">CAS Number 64-17-5</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Hydrochloric acid (37%)</td>
			<td style="width:96px;">VWR</td>
			<td style="width:114px;">PRLSMC310066</td>
			<td style="width:89px;">CAS Number 7647-01-0</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">L-Lysine (crystallized, &#8805;98.0% (NT))</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">62840</td>
			<td style="width:89px;">CAS Number 56-87-1</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Nitric acid (65%)</td>
			<td style="width:96px;">Merck</td>
			<td style="width:114px;">100456</td>
			<td style="width:89px;">CAS Number 7697-37-2</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Nitrobenzene</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">8.06770</td>
			<td style="width:89px;">CAS Number 98-95-3</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Potassium hydroxide</td>
			<td style="width:96px;">Fisher</td>
			<td style="width:114px;">10448990</td>
			<td style="width:89px;">CAS Number 1310-58-3</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Potassium tetrachloropalladate (II) (98%)</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">205796</td>
			<td style="width:89px;">CAS Number 10025-98-6</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Silver nitrate (ACS reagent, &#8805;99.0%)</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">209139</td>
			<td style="width:89px;">CAS Number 7761-88-8</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Sodium borohydride (fine granular for synthesis)</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">8.06373</td>
			<td style="width:89px;">CAS Number 16940-66-2</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:427px;">Zirconium (IV) oxide (nanopowder, &#60;100 nm particle size (TEM))</td>
			<td style="width:96px;">Sigma-Aldrich</td>
			<td style="width:114px;">544760</td>
			<td style="width:89px;">CAS Number 1314-23-4</td>
		</tr>
	</tbody>
</table>

preparation of silver-palladium alloyed nanoparticles for plasmonic catalysis under visible-light illumination

Plazmon nanopartiküllerde (NP) lokalize yüzey plazmon rezonansı (LSPR) çeşitli moleküler dönüşümlerin seçiciliğini hızlandırabilir ve kontrol edebilir. Bu, bu aralıklarda LSPR ekscitasyonunu destekleyen plazmonik nanopartiküller katalizör olarak kullanılırken reaksiyonları yönlendirmek ve kontrol etmek için sürdürülebilir bir girdi olarak görünür veya neredeyse IR ışığının kullanılması için olanaklar sunar. Ne yazık ki, paladyum (Pd) gibi birkaç katalitik metal için durum böyle değildir. Bu sınırlamayı aşmak için bir strateji plazmonik ve katalitik metaller içeren bimetalik NP'ler istihdam etmektir. Bu durumda, plazmonik metaldeki LSPR çıkarılması, katalitik bileşen tarafından yönlendirilen dönüşümleri hızlandırmaya ve kontrol etmeye katkıda bulunabilir. Burada bildirilen yöntem, plazmonik katalitik bir sistem görevi gören ZrO2'de (Ag-Pd/ZrO2)desteklenen bimetalik gümüş-paladyum (Ag-Pd) NP'lerin sentezine odaklanmaktadır. NP'ler, ZrO 2 desteğine karşılık gelen metal öncüllerinin birlikte emprenye edilmesi ve ardından doğrudan ZrO2 desteğinde bimetalik NP'lerin oluşumuna yol açan eşzamanlı azaltma ile hazırlanmıştır. Ag-Pd/ZrO2 NP'ler daha sonra LED lambalar tarafından 425 nm aydınlatmanın altındaki nitrobenzenin azaltılması için plazmonik katalizörler olarak kullanıldı. Gaz kromatografisi (GC) kullanılarak, plazmonik olmayan Pd'yi plazmonik metal Ag ile alaşımladıktan sonra LSPR uyarımı altında gelişmiş katalitik performans ve seçicilik kontrolünü gösteren, karanlık ve açık ışınlama koşulları altında azaltma reaksiyonunun dönüşümü ve seçiciliği izlenebilir. Bu teknik, çok çeşitli moleküler dönüşümlere ve NPs kompozisyonlarına uyarlanabilir, bu da farklı kataliz türlerinin plazmonik katalitik aktivitesinin dönüşüm ve seçicilik açısından karakterizasyonu için yararlı hale getirir.

Şekil 1A, saf ZrO 2 oksit (solda) ve Ag-Pd/ZrO 2 NPs (sağda) içeren katı örneklerin dijital fotoğraflarını göstermektedir. Beyazdan (ZrO2'de)kahverengiye (Ag-Pd/ZrO2)olan bu renk değişimi, Ag-Pd NP'lerin ZrO2 yüzeyindeki birikmesine ilişkin ilk nitel kanıtları sağlar. Şekil 1B, Ag-Pd/ZrO 2 NP'lerin (mavi iz) yanı sıra ZrO2 (siyah iz) ve Ag/ZrO2 NP'lerden (kırmızı i...

Watch this Scientific Journal Video about Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination at JoVE.com

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

Burada sunulan ZrO 2 (Ag-Pd/ZrO2)üzerinde desteklenen gümüş-paladyum (Ag-Pd) alaşımlı nanopartiküllerin(NPs) sentezi için bir protokoldür. Bu sistem, moleküler dönüşümleri hızlandırmak ve kontrol etmek için görünür ışık ışınlamadan enerji toplanmasına izin verir. Bu, Ag-Pd/ZrO2 NPs tarafından katalİze edilen ışık ışınlama altında nitrobenzen azaltma ile gösterilmiştir.

Görünür-Işık Aydınlatması Altında Plazmonik Kataliz için Gümüş-Paladyum Alaşımlı Nanopartiküllerin Hazırlanması

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular ...

preparation-silver-palladium-alloyed-nanoparticles-for-plasmonic

Research

JoVE Journal

Chemistry

5.4K Görüntüleme.  University of Helsinki. Burada sunulan ZrO 2 (Ag-Pd/ZrO2)üzerinde desteklenen gümüş-paladyum (Ag-Pd) alaşımlı nanopartiküllerin(NPs) sentezi için bir protokoldür. Bu sistem, moleküler dönüşümleri hızlandırmak ve kontrol etmek için görünür ışık ışınlamadan enerji toplanmasına izin verir. Bu, Ag-Pd/ZrO2 NPs tarafından katalİze edilen ışık ışınlama altında nitrobenzen azaltma ile gösterilmiştir.

Video: Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template&#39;s channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

This article describes the preparation of well-ordered nickel nanofoams via electroless metal deposition onto nanoporous templates obtained from self-assembled diblock copolymer based supramolecules.

Buradaki iki bloklu kopolimer Supramolecules ikinci Gyroid Nikel Nanoyapılar

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, ...

Kimya

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan &#948; solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials&#39; morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by St&#246;ber&#39;s methods, which have smooth surfaces.

Silica nanoparticles were prepared using acid-catalysis of a siloxane precursor and microwave-assisted synthetic techniques resulting in the controlled growth of nanomaterials ranging from 30-250 nm in diameter. The growth dynamics can be controlled by varying the initial silicic acid concentration, time of the reaction, and temperature of reaction.

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle ...

Synthesis of Immunotargeted Magneto-plasmonic Nanoclusters

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications including contrast enhancement in novel magnetomotive imaging modalities, simultaneous capture&#160;and detection of circulating tumor cells (CTCs),&#160;and multimodal molecular imaging combined with photothermal therapy of cancer cells. These applications have stimulated significant interest in development of protocols for synthesis of magneto-plasmonic nanoparticles with optical absorbance in the near-infrared (NIR) region and a strong magnetic moment. Here, we present a novel protocol for synthesis of such hybrid nanoparticles that is based on an oil-in-water microemulsion method. The unique feature of the protocol described herein is synthesis of magneto-plasmonic nanoparticles of various sizes from primary blocks which also have magneto-plasmonic characteristics. This approach yields nanoparticles with a high density of magnetic and plasmonic functionalities which are uniformly distributed throughout the nanoparticle volume. The hybrid nanoparticles can be easily functionalized by attaching antibodies through the Fc moiety leaving the Fab portion that is responsible for antigen binding available for targeting.

Here, we describe a protocol for synthesis of magneto-plasmonic nanoparticles with a strong magnetic moment and a strong near-infrared (NIR) absorbance. The protocol also includes antibody conjugation to the nanoparticles through the Fc moiety for various biomedical applications which require molecular specific targeting.

Immunotargeted sentezi Magneto-plasmonik nanoklastırlar

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications ...

Preparation and Characterization of SDF-1&#945;-Chitosan-Dextran Sulfate Nanoparticles

Chitosan (CS) and dextran sulfate (DS) are charged polysaccharides (glycans), which form polyelectrolyte complex-based nanoparticles when mixed under appropriate conditions. The glycan nanoparticles are useful carriers for protein factors, which facilitate the in vivo delivery of the proteins and sustain their retention in the targeted tissue. The glycan polyelectrolyte complexes are also ideal for protein delivery, as the incorporation is carried out in aqueous solution, which reduces the likelihood of inactivation of the proteins. Proteins with a heparin-binding site adhere to dextran sulfate readily, and are, in turn, stabilized by the binding. These particles are also less inflammatory and toxic when delivered in vivo. In the protocol described below, SDF-1&#945; (Stromal cell-derived factor-1&#945;), a stem cell homing factor, is first mixed and incubated with dextran sulfate. Chitosan is added to the mixture to form polyelectrolyte complexes, followed by zinc sulfate to stabilize the complexes with zinc bridges. The resultant SDF-1&#945;-DS-CS particles are measured for size (diameter) and surface charge (zeta potential). The amount of the incorporated SDF-1&#945; is determined, followed by measurements of its in vitro release rate and its chemotactic activity in a particle-bound form.

Preparation and Characterization of SDF-1&amp;#945;-Chitosan-Dextran Sulfate Nanoparticles

The objective of this protocol is to incorporate SDF-1&#945;, a stem cell homing factor, into dextran sulfate-chitosan nanoparticles. The resultant particles are measured for their size and zeta potential, as well as the content, activity, and in vitro release rate of SDF-1&#945; from the nanoparticles.

SDF-1α-Kitosan-Dekstran Sülfat nano partiküllerin hazırlanması ve Karakterizasyonu

Chitosan (CS) and dextran sulfate (DS) are charged polysaccharides (glycans), which form polyelectrolyte complex-based nanoparticles when mixed under ...

A Simple Method for the Size Controlled Synthesis of Stable Oligomeric Clusters of Gold Nanoparticles under Ambient Conditions

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like oligomeric clusters of these yellow nanoparticles of narrow size distribution are synthesized under ambient conditions via two methods. The delay-time method controls the number of subunits in the oligoclusters by varying the time between the addition of HAuCl4 to alkaline solution and the subsequent addition of reducing agent, NaSCN. The yellow oligoclusters produced range in size from ~3 to ~25 nm. This size range can be further extended by an add-on method utilizing hydroxylated gold chloride (Na+[Au(OH4-x)Clx]-) to auto-catalytically increase the number of subunits in the as-synthesized oligocluster nanoparticles, providing a total range of 3 nm to 70 nm. The crude oligocluster preparations display narrow size distributions and do not require further fractionation for most purposes. The oligoclusters formed can be concentrated &#62;300 fold without aggregation and the crude reaction mixtures remain stable for weeks without further processing. Because these oligomeric clusters can be concentrated before derivatization they allow expensive derivatizing agents to be used economically. In addition, we present two models by which predictions of particle size can be made with great accuracy.

We describe a simple method for producing highly stable oligomeric clusters of gold nanoparticles via the reduction of chloroauric acid (HAuCl4) with sodium thiocyanate (NaSCN). The oligoclusters have a narrow size distribution and can be produced with a wide range of sizes and surface coats.

Ortam Koşullarında Altın Nanopartiküller Kararlı Oligomerik Kümeleri Boyut Kontrollü Sentezi için Basit Bir Yöntem

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like ...

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism.

A method for the atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst is described.

Bir görünür ışık fotokatalistinin olarak Perylene kullanarak Fonksiyonlu Vinil Monomer Atom Transfer Radikal Polimerizasyonu

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The ...

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

HKUST-1 vanilin Sentezi için bir heterojen katalizör halinde

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Photoredox Katalizörü kullanarak görünür ışık aracılığı ile dispersiyon polimerleştirilmesi ile solucan gibi miseller Facile sentezi

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared according to the methodology developed by surface organometallic chemistry (SOMC). In this framework, catalytic cycles can be determined by isolating crucial intermediates. All air-sensitive materials are handled under inert atmosphere (using gloveboxes or a Schlenk line) or high vacuum lines (HVLs, &#60;10-5 mbar). The preparation of SiO2-700 (silica dehydroxylated at 700 &#176;C) and subsequent applications (the grafting of complexes and catalytic runs) requires the use of HVLs and double-Schlenk techniques. Several well-known characterization methods are used, such as Fourier-transform infrared spectroscopy (FTIR), elemental microanalysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR), and state-of-the-art dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS). FTIR and elemental microanalysis permit scientists to establish the grafting and its stoichiometry. 1H and 13C SSNMR allows the structural determination of the hydrocarbon ligands coordination sphere. DNP SENS is an emerging powerful technique in solid characterization for the detection of poorly sensitive nuclei (15N, in our case). SiO2-700 is treated with about one equivalent of the metal precursor compared to the amount of surface silanol (0.30 mmol&#183;g-1) in pentane at room temperature. Then, volatiles are removed, and the powder samples are dried under dynamic high vacuum to afford the desired materials [(&#8801;Si-O-)Hf(&#951;2&#960;-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)]. After a thermal treatment under high vacuum, the grafted complex is converted into metal imido silica complex [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)]. [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] effectively promotes the metathesis of imines, using the combination of two imine substrates, N-(4-phenylbenzylidene)benzylamine, or N-(4-fluorobenzylidene)-4-fluoroaniline, with N-benzylidenetert-butylamine as substrates. A significantly lower conversion is observed with the blank runs; thus, the presence of the imido group in [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is correlated to the catalytic performance.

A new group IV metal catalyst for imine metathesis is prepared by grafting amine metal complex onto dehydroxylated silica. Surface metal fragments are characterized using FT-IR, elemental microanalysis, and solid-state NMR spectroscopy. Further dynamic nuclear polarization surface enhanced NMR spectroscopy experiments complement the determination of the coordination sphere.

Yüzey Organometalik Kimya metodolojisini kullanan Silika Destekli Katalizörler tarafından Imine Metatez

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared ...

Performing Spectroscopy on Plasmonic Nanoparticles with Transmission-Based Nomarski-Type Differential Interference Contrast Microscopy

Differential interference contrast (DIC) microscopy is a powerful imaging tool that is most commonly employed for imaging microscale objects using visible-range light. The purpose of this protocol is to detail a proven method for preparing plasmonic nanoparticle samples and performing single particle spectroscopy on them with DIC microscopy. Several important steps must be followed carefully in order to perform repeatable spectroscopy experiments. First, landmarks can be etched into the sample substrate, which aids in locating the sample surface and in tracking the region of interest during experiments. Next, the substrate must be properly cleaned of debris and contaminants that can otherwise hinder or obscure examination of the sample. Once a sample is properly prepared, the optical path of the microscope must be aligned, using Kohler Illumination. With a standard Nomarski style DIC microscope, rotation of the sample may be necessary, particularly when the plasmonic nanoparticles exhibit orientation-dependent optical properties. Because DIC microscopy has two inherent orthogonal polarization fields, the wavelength-dependent DIC contrast pattern reveals the orientation of rod-shaped plasmonic nanoparticles. Finally, data acquisition and data analyses must be carefully performed. It is common to represent DIC-based spectroscopy data as a contrast value, but it is also possible to present it as intensity data. In this demonstration of DIC for single particle spectroscopy, the focus is on spherical and rod-shaped gold nanoparticles.

The goal of this protocol is to detail a proven approach for the preparation of plasmonic nanoparticle samples and for performing single particle spectroscopy on them with differential interference contrast (DIC) microscopy.