Hasil Pencarian  ::  Simpan CSV :: Kembali

Abstrak :
CO2 merupakan gas yang inert, tidak beracun, tidak mudah terbakar, dan menjadi gas penyumbang terbesar dalam efek rumah kaca yang menyebabkan suhu permukaan bumi naik. Di sisi lain, kelimpahannya yang tinggi di alam menjadikan CO2 sebagai sumber karbon yang potensial dalam sintesis fine chemicals. Dalam penelitian ini dilakukan studi reaksi karboksilasi fenilasetilena dengan CO2 menggunakan katalis logam Ni terimpregnasi pada support karbon mesopori. Karbon mesopori telah berhasil disintesis dengan metode soft template menggunakan Pluronik F127 sebagai pembentuk pori, formaldehida dan phloroglucinol sebagai sumber karbon, dan HCl sebagai katalis asam. Material ini dikarakterisasi dengan FTIR, XRD, SEM, dan BET. Spektra FTIR dari karbon mesopori sebelum karbonisasi memiliki puncak serapan 3500 2800 cm-1 yang menunjukkan adanya stretching C-H dan stretcing O-H dari phloroglucinol dan formaldehida. Sedangkan setelah karbon mesopori dikarbonisasi, puncak serapan pada bilangan gelombang tersebut hilang. Karakterisasi dengan XRD menunjukkan adanya dua puncak pada 2 yakni 24,26o dan 42,76o yang menandakan puncak khas dari karbon mesopori. Analisis luas permukaan dengan BET menghasilkan isoterm adsorpsi N2 pada karbon mesopori yang menunjukkan adanya hystersis loop pada rentang P/Po sekitar 0,4-0,9 yang merupakan karakter dari karbon mesopori. Karbon mesopori hasil sintesis memiliki distribusi ukuran pori sebesar 7.2 nm yang termasuk dalam rentang material mesopori 2-50 nm . Karakterisasi dengan SEM menunjukkan bentuk yang datar dengan ukuran kristal beragam. Modifikasi support dilakukan dengan cara impregnasi logam Ni ke dalam karbon mesopori Ni@MC . Katalis Ni@MC digunakan sebagai katalis dalam reaksi karboksilasi fenilasetilena dengan CO2. Reaksi dilakukan dalam reaktor batch dengan kondisi reaksi yang bervariasi, yakni suhu 25oC, 50oC, 85oC dan waktu 8 jam, 12 jam, dan 16 jam. Hasil analisis campuran produk dengan HPLC menunjukkan terbentuknya asam sinamat sebesar 1,52 pada sampel 85oC 8jam, 2,83 pada sampel 85oC 12jam, dan 0,62 pada sampel 85oC 16jam. ...... CO2 is an inert, non toxic, non flammable, and the largest contributor gas to greenhouse gases causing the earth 39 s surface temperature to rise. Its high abundance in nature makes CO2 a potential carbon source in fine chemical synthesis. In this research, carboxylation reaction of phenylacetylene with CO2 has been studied using an impregnated nickel catalyst on mesoporous carbon support. Mesoporous carbon has been successfully synthesized by soft template method using Pluronic F127 as pore forming, formaldehyde and phloroglucinol as carbon source, and HCl as acid catalyst. This material was characterized by FTIR, XRD, SEM, and BET analysis. The FTIR spectra of the mesoporous carbon before carbonization had an absorption peak of 3500 2800 cm 1 indicating the presence of stretching C H and stretching O H of phloroglucinol and formaldehyde. Meanwhile after carbonization, those peaks disappear. Characterization with XRD shows the presence of two peaks at 2 24.26 and 42.76 which denotes the typical peak of mesoporous carbon. BET Surface Area Analysis gave N2 adsorption isotherm on mesoporous carbon indicating a hysterysis loop in the P Po range 0.4 0.9 which is a character of mesoporous carbon. Synthesized mesoporous carbon had pore size distribution of 7.2 nm which is included in the mesoporous material range 2 50 nm . Characterization with SEM shows a flat shape with varying crystal sizes. Modification of support has been conducted by impregnation of Ni metal into mesoporous carbon Ni MC . The Ni MC catalyst was used as a catalyst in the carboxylation reaction of phenylacetylene with CO2. The reactions were carried out in a batch reactor under various reaction conditions at reaction temperature of 25oC, 50oC, and 85oC and for over 8, 12, and 16 hours. HPLC analysis of the product mixtures shows that cinnamic acid was formed with 1,52 yield in 85oC 8h sample, 2,83 yield in 85oC 12h sample, and 0,62 yield in 85oC 16h sample.

Abstrak :
Carbon dioxide is a renewable C1 resource for synthesis chemicals. CO2 in carboxylation reactions requires catalysts Ni complex for CO2 activation. However, the use of Ni complex homogeneous catalysts in the reaction is still less efficient due to the difficult in separating the product and catalyst. Therefore, it is necessary to heterogenize the Ni complex in solid supporting such as mesoporous carbon. In this research, a carboxylation reaction with CO2 was tested using a Ni catalyst that was functionalized with phenanthroline (phen) ligand impregnated on the solid support of mesoporous carbon. Soft template method has been successfully used in mesoporous carbon synthesis with phloroglucinol and formaldehyde prekursors as a carbon source, Pluronic F127 as a structural directing agent, and HCl as an acid catalyst. Modification of the catalyst was carried out by impregnation of Ni from Ni(NO3)2.6H2O which was then functionalized with phenanthroline (phen) ligands into mesoporous carbon to form Ni-phen/MC catalysts. Mesoporous carbon material (MC) and Ni-phen/MC are characterized by FT-IR, XRD, SEM-EDX, and SAA. The results of SAA characterization showed that the pore diameter of MC was 6.7174 nm and Ni-phen/MC was 5.08 nm which indicate that the material was mesoporous. Ni-phen/MC material was then used as a heterogeneous catalyst in the carboxylation reaction of phenylacetylene with CO2. The reaction were carried out in several variations of conditions, temperature variations (25oC, 50oC and 75oC), time variations (4 hours, 8 hours and 16 hours), variations in catalyst types (MC, Ni-phen and Ni-phen/MC). Based on the results of the reaction, the optimum conditions was obtained at 25oC for 8 hour of reaction time using Ni-phen/MC catalyst. The main product of the carboxylation reaction is identified by the HPLC instrument, while the remaining catalyst that has been used in the reaction was identified using the FT-IR instrument.
Carbon dioxide is a renewable C1 resource for synthesis chemicals. CO2 in carboxylation reactions requires catalysts Ni complex for CO2 activation. However, the use of Ni complex homogeneous catalysts in the reaction is still less efficient due to the difficult in separating the product and catalyst. Therefore, it is necessary to heterogenize the Ni complex in solid supporting such as mesoporous carbon. In this research, a carboxylation reaction with CO2 was tested using a Ni catalyst that was functionalized with phenanthroline (phen) ligand impregnated on the solid support of mesoporous carbon. Soft template method has been successfully used in mesoporous carbon synthesis with phloroglucinol and formaldehyde prekursors as a carbon source, Pluronic F127 as a structural directing agent, and HCl as an acid catalyst. Modification of the catalyst was carried out by impregnation of Ni from Ni(NO3)2.6H2O which was then functionalized with phenanthroline (phen) ligands into mesoporous carbon to form Ni-phen/MC catalysts. Mesoporous carbon material (MC) and Ni-phen/MC are characterized by FT-IR, XRD, SEM-EDX, and SAA. The results of SAA characterization showed that the pore diameter of MC was 6.7174 nm and Ni-phen/MC was 5.08 nm which indicate that the material was mesoporous. Ni-phen/MC material was then used as a heterogeneous catalyst in the carboxylation reaction of phenylacetylene with CO2. The reaction were carried out in several variations of conditions, temperature variations (25oC, 50oC and 75oC), time variations (4 hours, 8 hours and 16 hours), variations in catalyst types (MC, Ni-phen and Ni-phen/MC). Based on the results of the reaction, the optimum conditions was obtained at 25oC for 8 hour of reaction time using Ni-phen/MC catalyst. The main product of the carboxylation reaction is identified by the HPLC instrument, while the remaining catalyst that has been used in the reaction was identified using the FT-IR instrument.

Abstrak :

Pengembangan metodologi sintetis yang memanfaatkan karbon dioksida sebagai sumber karbon C1 sangat diperlukan untuk sintesis bahan kimia yang berguna, mengingat dampak negatif lingkungan dari peningkatan kadar CO₂ di atmosfer. Dalam penelitian ini, telah dilakukan studi reaksi karboksilasi fenilasetilena dengan CO₂ menggunakan katalis kompleks Ni terimobilisasi pada support karbon mesopori. Karbon mesopori telah berhasil disintesis dengan metode soft template menggunakan Pluronik F127 sebagai pembentuk pori, formaldehida dan phloroglucinol sebagai sumber karbon, dan HCl sebagai katalis asam. Material ini dikarakterisasi dengan FTIR, XRD, SEM, dan BET. Modifikasi support dilakukan dengan cara imobilisasi kompleks Ni ke dalam karbon mesopori (kompleks Ni/MC). Katalis kompleks Ni/MC digunakan sebagai katalis dalam reaksi karboksilasi fenilasetilena dengan CO₂. Reaksi dilakukan dalam reaktor dengan kondisi reaksi yang bervariasi, yakni variasi suhu (25^oC, 50^oC, 75^oC), variasi waktu (4 jam, 8 jam, dan 16 jam). Produk reaksi karboksilasi ini kemudian dianalisis dengan menggunakan HPLC untuk menentukan persen konversi. Analisis FTIR Ni(bpy)/MC menunjukan puncak pada panjang gelombang 1385 cm^-1  (C-N stretching). Analisis XRD menunjukan difraksi MC pada 24.67º dan 43.26º dan Ni(bpy)/MC pada 23.53º dan 43.56º. Analisis BET memberi informasi luas permukaan, distribusi pori, dan volume pori sebesar MC sebesar 288.7242 m²/g, 3.6136 nm, dan 0.5766 cc/g, dan Ni(bpy)/MC sebesar 348,9490 m²/g, 3.1157 nm, dan 0.3291cc/g. Analisis SEM-EDX memberi informasi morfologi permukaan MC terimobilisasi kompleks bipiridin dengan persen loading sebesar 3.26%. Analisis adsorpsi menunjukan Ni(bpy)/MC memiliki kemampuan adsorpsi CO₂ yang lebih tinggi dari MC. Konversi terbesar didapat dari Ni(bpy)/MC dengan persen konversi sebesar 94.5911% dan luas area produk sebesar 25.3846 mAU.

 

---

The development of a synthetic methodology that utilizes carbon dioxide as a source of C1 carbon is indispensable for the synthesis of useful chemicals, due to the negative effects to environmental by increased levels of CO₂ in the atmosphere. In this research, carboxylation reaction of phenylacetylene with CO₂ has been carried out using nickel immobilized at mesoporous carbon as catalyst support. Mesoporous carbon has been successfully synthesized using soft template method with Pluronik F127 as a pore-forming, formaldehyde and phloroglucinol as carbon source, and HCl as acid catalyst. Material was characterized by FTIR, XRD, SEM, and BET. Modification of support was done by immobilizing nickel complex at mesoporous carbon (Ni complex/MC). Ni complex/MC was then used as a catalyst in carboxylation reaction of phenylacetylene with CO₂. The reactions were carried out in reactor with various conditions, such as temperature (25^oC, 50^oC, 75^oC), and time (4 hours, 8 hours, 16 hours). The result of carboxylation reactions were analyzed by HPLC to determine conversion. FTIR analysis of Ni(bpy)/MC showed a peak at a wavelength of 1385 cm^-1 (C-N stretching). XRD analysis showed MC diffraction at 24.67º and 43.26º and Ni(bpy)/MC at 23.53º and 43.56º. BET analysis gave information about the surface area, pore distribution, and pore volume of MC of 288.7242 m²/g, 3.6136 nm, and 0.5766 cc/g, and Ni(bpy)/MC of 348.9490 m²/g, 3.1157 nm, and 0, 3291 cc/g. SEM-EDX analysis gave information about the surface morphology of the MC is immobilized by the bipyridine complex with loading of 3.26%. Adsorption analysis shows that Ni(bpy)/MC has higher CO₂ adsorption ability than MC. The highest conversion is shown by Ni(bpy)/MC 8h at 25ºC with conversion of 94.5911% and product area of 25.3846 mAU.

Abstrak :
Konsentrasi CO2 di dalam atmosfer yang terus meningkat menjadi perhatian bagi peneliti untuk mengkonversi CO2 menjadi senyawa yang lebih ramah lingkungan serta bermanfaat. Dalam penelitian ini, dilakukan studi adsorpsi dan reaksi karboksilasi untuk mengkonversi CO2 menggunakan substrat fenilasetilena, katalis heterogen Cu/MC, dan basa Cs2CO3 pada suhu 75˚C. Hasil sintesis karbon mesopori (MC) dikarakterisasi dengan FTIR dan SEMEDX- Mapping. Hasil FTIR MC memperlihatkan proses karbonisasi yang belum sempurna, ditandai dengan adanya peak C-O dan O-H. Namun hasil SEM-EDX-Mapping memperlihat struktur pori yang cukup seragam dengan komposisi unsur C mencapai 86.01% dan unsur O mencapai 13.99%. Hasil sintesis Cu/MC dikarakterisasi dengan FTIR dan SEM-EDX yang menunjukkan bertambahnya gugus C=C terkonjugasi sehingga komposisi C meningkat menjadi 82,34%, sementara komposisi O sekitar 15,34%, dan komposisi Cu sekitar 02,32%. Hasil karboksilasi fenilasetilena dengan CO2 menunjukan terbentuknya produk asam-3-fenil propiolat namun dalam jumlah yang sangat sedikit. Dalam penelitian ini juga diuji sifat adsorpsi fenilasetilena pada Cu/MC dan adsorpsi fenilasetilena pada MC dengan adanya penambahan basa Cs2CO3. Berdasarkan hasil HPLC uji adsorpsi fenilasetilena, diketahui bahwa adsorpsi fenilasetilena pada Cu/MC lebih baik daripada adsorpsi fenilasetilena pada MC. ......Concentration of CO2 in the atmosphere that continues to increase is a concern for researchers to convert CO2 into compounds that are more environmentally friendly and useful. In this research, study of phenylethethylene adsorption and carboxylation reaction were carried out. The carboxylation reaction to convert CO2 required phenylacetylene as substrate, Cu/MC as heterogeneous catalyst, and Cs2CO3 as base (source of nucleophile). The carboxylation reactions were carried out at 75˚C. The results of mesoporous carbon synthesis (MC) were characterized by FTIR and SEM-EDX-Mapping. The FTIR MC results show that the carbonization process is not perfect, characterized by the peak C-O and O-H. But the SEM-EDX-Mapping results show a fairly uniform pore structure with the composition of element C reaching 86.01% and element O reaching 13.99%. The results of Cu/MC synthesis were characterized by FTIR and SEM-EDX which showed an increase in the conjugated C = C group so that the composition of C increased to 82.34%, while the composition of O was around 15.34%, and the composition of Cu was around 02.32%. The carboxylation of phenylacetylene with CO2 showed the formation of acid-3-phenyl propiolic products but in very small amounts. In this study also tested the properties of phenylacetylene adsorption on Cu/MC and phenylacetylene adsorption on MC with the addition of Cs2CO3 base. Based on the results of HPLC phenylacetylene adsorption test, it is known that the adsorption of phenylacetylene in Cu/MC is better than phenylacetylene adsorption on MC.

Abstrak :
Karbon dioksida merupakan gas rumah kaca dengan kelimpahan yang tinggi di bumi. Buruknya dampak yang ditimbulkan oleh gas CO2 menjadi tantangan sendiri bagi manusia untuk memanfaatkan CO2 sebagai bahan baku yang nantinya akan menghasilkan produk bermanfaat yang memiliki nilai tambah. Pada kenyataannya, selain memiliki dampak buruk yang buruk, CO2 ternyata memiliki manfaat yakni sebagai sumber C1 reaksi organik, salah satunya reaksi karboksilasi. Pada penelitian ini, nanopartikel NiAg berhasil disintesis dengan PVP sebagai capping agent dan NaBH4 yang berperan sebagai reduktor untuk menghasilkan katalis bimetalik yang digunakan dalam reaksi karboksilasi difenilasetilan dengan CO2. Analisis XRD menunjukkan NiAg yang telah disintesis menunjukkan terbentuknya logam Ni(0) dan Ag(0). Analisis SEM-EDX dari NiAg menunjukkan NiAg memiliki karakteristik yang baik dibuktikan dengan persebaran logam Ni dan logam Ag yang tersebar merata yang menandakan katalis bimetalik terbentuk. Analisis TEM menunjukkan NiAg memiliki ukuran rata-rata partikel sebesar 7,69 nm yang termasuk ke dalam nanomaterial. Uji katalitik dilakukan untuk beberapa katalis pada reaksi karboksilasi difenilasetilena dengan CO2 dengan lima variasi waktu, lima variasi suhu, dan penggunaan DBU sebagai pelarut tambahan. Analisis HPLC menunjukkan hasil reaksi karboksilasi difenilasetilena dengan CO2 terbaik dengan persen yield sebesar 7,1% dengan bantuan katalis NiAg (1:1) pada suhu 50°C selama 4 jam pada medium DMF dengan adanya penambahan DBU sebanyak (4 mmol, 5 ekuivalen) ......Carbon dioxide is the most abundant greenhouse gas in the earth’s atmosphere. While most of the focus on CO2 is on its bad impact, it can also be a challenging for human to utilize CO2 as a raw material that will produce useful products. However, aside from the negative effects of CO2, it has been used as a source of C1 in organic reactions, for example, carboxylation reactions. The synthesis was based on the reduction of Ni and Ag ions with sodium borohydride in the presence of PVP as a capping agent. NiAg as a bimetallic catalyst used in the carboxylation reaction of diphenylacetylene with CO2. Based on the results of XRD analysis for NiAg, there are diffraction indicating that the Ni(0) and Ag(0) was successfully formed. Bimetallic catalyst was successfully formed with Ni and Ag species was evenly distributed based on SEM-EDX analysis. The size of particles were determined using TEM test. The obtained nanoparticles had an average size of 7,69 nm. The Catalytic test of NiAg on diphenylacetylene carboxylation with CO2 was accomplished at five time variations, five temperature variations, and the used of DBU as an additional solvent. HPLC analysis shows the best results of the carboxylation of diphenylacetylene with CO2 obtained at reaction temperature of 50°C and time of 4 hour using NiAg (1:1) catalyst in DMF medium and in the presence of (4 mmol, 5 eq) of DBU. The optimum reaction on diphenylacetylene carboxylation resulting phenylmaleic as a product with percentage yield of 7,1%.

Abstrak :
Sintesis karbon mesopori secara soft template dan hard template dari berbagai prekursor karbon; phloroglucinol, glukosa, dan hidrolisat tandan kosong kelapa sawit (TKKS) telah dilakukan. Pluronic F127 dan silica gel digunakan sebagai cetakan pada sintesis karbon mesopori soft template dan hard template, secara berturut-turut. Material karbon mesopori kemudian diimpregnasi dengan logam Ni dan direduksi menggunakan gas H2 sehingga membentuk Ni/mesoporous carbon (Ni/MC). Karakterisasi material dengan FTIR menunjukkan bahwa gugus organik pada soft templated mesoporous carbon (ST MC) menghilang setelah proses karbonisasi dan pada hard templated mesoporous carbon (HT MC) setelah proses desilikasi, mengindikasikan bahwa proses tersebut efektif dalam penghilangan template yang digunakan. Berdasarkan analisis SEM, material karbon memiliki morfologi seperti serpihan dengan tambahan sebaran butiran halus setelah impregnasi. Berdasarkan hasil analisis XRD untuk ST MC dan HT MC, terdapat difraksi khas karbon grafit pada 2θ 25⁰ dan 44⁰. Kemudian terdapat tambahan difraksi setelah impregnasi pada 2θ 45⁰ dan 52⁰ yang bersesuaian dengan Ni(0), mengindikasikan bahwa impregnasi berhasil dilakukan. Analisa luas permukaan menunjukkan bahwa material karbon memiliki luas permukaan dan distribusi pori yang bervariasi. Material selanjutnya digunakan sebagai katalis dalam reaksi karboksilasi fenilasetilena dengan karbon dioksida. Analsis HPLC menunjukkan hasil terbaik pada suhu reaksi 85⁰C dan waktu reaksi 8 jam dengan menggunakan katalis HT Ni/MC phloroglucinol dan garam MgCl2. Yield pembentukan produk asam fenil propiolat pada kondisi tersebut adalah 2,2 %.

---

Synthesis of soft templated and hard templated mesoporous carbon from various carbon precursors; phloroglucinol, glucose, and empty palm oil shell hidrolisate, has been conducted successfully. Pluronic F127 and silica gel were used as template in the sythesis of soft and hard templated mesoporous carbon, respectively. The materials were then impregnated with Ni and reduced under H2 flow to form Ni/Mesoporous Carbon (Ni/MC). Characterization with FTIR shows that the organic groups in Soft Templated Mesoporous Carbon (ST MC) disappear after the carbonization process and in Hard Templated Mesoporous Carbon (HT MC) after the desilication process, indicating that the process is effective in template removal. Based on the SEM analysis, carbon materials have flakes-like morphology with the addition of fine grain spreads after impregnation. Based on the results of XRD analysis for ST MC and HT MC, there are a typical graphite carbon diffractions on 2θ of 25 and 44 ⁰. There are also additional diffraction peaks at 2θ of 45 and 52⁰ after impregnation which correspond with Ni(0), indicating that the Ni impregnation was successfully performed. The analysis of the surface area indicates that carbon materials have various surface area and pore distribution. The materials are subsequently used as a catalyst in the carboxylation reaction of phenylacetylene with carbon dioxide. HPLC analysis shows the best resultis obtained at reaction temperature of 85 ⁰ _C and time of 8 hour using MgCl2 salt and HT Ni/MC phloroglucinol catalyst. Yield of phenyl propiolic acid formation as product of carboxylation obtained on optimum condition is 2,2%.

Abstrak :
ABSTRAK
Grafena adalah alotrop karbon yang kristalnya tersusun secara heksagonal dengan hibridisasi sp2. Grafena dan nanokompositnya dengan berbagai logam transisi telah dikembangkan untuk berbagai aplikasi, mulai dari sensor, elektronik, energi hingga bidang biomedis. Selain itu, nanokomposit berbasis graphene juga banyak dikembangkan untuk aplikasinya sebagai katalis karena memiliki luas permukaan yang besar serta memiliki konduktivitas dan stabilitas yang baik. Pada penelitian ini, graphene oxide (rGO) tereduksi yang dimodifikasi dengan nanopartikel Ag disintesis sebagai katalis heterogen dalam reaksi karboksilasi antara fenilacetylene dan CO2. Karakterisasi nanokomposit AgNPs / graphene oxide tereduksi dilakukan dengan menggunakan Scanning Electron Microscopy - Spektroskopi sinar-X dispersif energi, Fourier Transform Infra Red, X-ray Powder Diffraction dan UV-Vis Spectroscopy. Berdasarkan hasil UV-Vis didapatkan puncak absorbansi pada panjang gelombang 253 nm yang menunjukkan adanya restorasi konjugasi elektronik pada permukaan rGO. Spektrum FTIR dari nanokomposit AgNPs / rGO menunjukkan penurunan intensitas absorbansi gugus hidroksil dan keton dibandingkan dengan spektrum oksida graphene, menunjukkan bahwa reduksi gugus fungsi yang mengandung oksigen telah berhasil dilakukan dengan menggunakan urea. Hasil XRD menunjukkan intensitas puncak pada 38.14o (111), 44.27o (200), 64.43o (220), 77.38o (311), menunjukkan bahwa nanopartikel Ag yang terbentuk memiliki kristalografi fcc. Hasil SEM-EDX menunjukkan nanopartikel Ag tersebar di permukaan rGO dengan persentase massa 38,57%. Reaksi karboksilasi dilakukan dalam reaktor batch dengan variasi basa dan suhu. Berdasarkan hasil analisis produk menggunakan HPLC, luas produk utama terbesar yang diperoleh dari reaksi menggunakan basa Na2CO3 adalah 204,1361 dan suhu 50oC adalah 128,2214. Sedangkan luas produk minor terbesar diperoleh dari reaksi menggunakan basa Cs2CO3 sebesar 6,2175 dan suhu 80 oC sebesar 18,3130.
ABSTRACT
Graphene is an allotrope of carbon whose crystals are arranged hexagonally by sp2 hybridization. Graphene and its nanocomposites with various transition metals have been developed for a wide range of applications, from sensors, electronics, energy to biomedical fields. In addition, graphene-based nanocomposites have also been widely developed for applications as catalysts because they have a large surface area and have good conductivity and stability. In this study, reduced graphene oxide (rGO) modified with Ag nanoparticles was synthesized as a heterogeneous catalyst in the carboxylation reaction between phenylacetylene and CO2. Characterization of reduced AgNPs / graphene oxide nanocomposites was performed using Scanning Electron Microscopy - Energy dispersive X-ray spectroscopy, Fourier Transform Infra Red, X-ray Powder Diffraction and UV-Vis Spectroscopy. Based on the UV-Vis results, the absorbance peak was obtained at a wavelength of 253 nm which indicated the presence of electronic conjugation restoration on the rGO surface. The FTIR spectrum of the AgNPs/rGO nanocomposite showed a decrease in the absorbance intensity of the hydroxyl and ketone groups compared to the graphene oxide spectrum, indicating that the reduction of oxygen-containing functional groups was successfully carried out using urea. XRD results showed peak intensities at 38.14o (111), 44.27o (200), 64.43o (220), 77.38o (311), indicating that the Ag nanoparticles formed had fcc crystallography. The SEM-EDX results showed that Ag nanoparticles were scattered on the surface of rGO with a mass percentage of 38.57%. The carboxylation reaction was carried out in a batch reactor with variations in base and temperature. Based on the results of product analysis using HPLC, the largest area of ​​the main product obtained from the reaction using the base Na2CO3 was 204.1361 and a temperature of 50oC was 128.2214. Meanwhile, the largest minor product area was obtained from the reaction using the base Cs2CO3 of 6.2175 and a temperature of 80 oC of 18.3130.

Abstrak :
Karbon dioksida adalah gas rumah kaca yang melimpah di atmosfer dan dapat menyebabkan pemanasan global. Konversi atau pemanfaatan CO2 menjadi bahan yang bernilai tambah dapat menjadi strategi untuk mengurangi emisi gas CO2 di atmosfer. Berbagai pendekatan reaksi untuk mengubah CO2 telah dipelajari, salah satunya reaksi karboksilasi. Pada penelitian ini, nanopartikel NiAg berhasil disintesis dengan bantuan CTAB sebagai capping agent dan NaBH4 sebagai agen pereduksi untuk menghasilkan katalis bimetalik. Analisis XRD menunjukkan puncak pada 38,13°, 44,37°, 64,54°, 77,41°, dan 81,62° yang menandakan terbentuknya logam Ag(0) dan Ni(0) pada nanopartikel NiAg. Analisis SEM-EDX menunjukkan morfologi NiAg berbentuk seperti butiran dengan permukaan yang kasar, serta persebaran logam Ni dan Ag yang merata. Analisis TEM menunjukkan ukuran rata-rata partikel NiAg sebesar 22,684 nm yang termasuk ke dalam nanomaterial. Nanopartikel NiAg hasil sintesis digunakan dalam reaksi karboksilasi fenilasetilena dengan CO2 dalam medium DMF dan DBU. Penambahan jumlah ekivalen DBU dilakukan untuk meningkatkan performa katalis dalam menghasilkan produk asam karboksilat dalam reaksi karboksilasi fenilasetilena dengan CO2. Analisis HPLC menunjukkan hasil optimum diperoleh dengan penambahan 10 ekivalen DBU pada temperatur 55 °C selama 4 jam dengan yield sebesar 0,5382% untuk asam fenilpropiolat dan 0,3459% untuk asam sinamat, serta konversi fenilasetilena mencapai 78,8452%. ......Carbon dioxide is a greenhouse gas abundant in the atmosphere and can cause global warming. Conversion or utilization of CO2 into value-added materials can be a strategy to reduce CO2 gas emissions in the atmosphere. Various reaction approaches to convert CO2 have been studied, one of which is the carboxylation reaction. In this study, NiAg nanoparticles were synthesized with CTAB as a capping agent and NaBH4 as a reducing agent to produce a bimetallic catalyst. XRD analysis of NiAg showed peaks at 38,13°, 44,37°, 64,54°, 77,41°, and 81,62°, indicating the formation of Ag(0) and Ni(0) metals. SEM-EDX analysis showed that NiAg morphology was granular with a rough surface, and the distribution of Ni and Ag metals was uniform. TEM analysis showed the average size of NiAg particles to be 22,684 nm, which belongs to the nanomaterial category. The synthesized NiAg nanoparticles was used in the carboxylation reaction of phenylacetylene with CO2 in the DMF and DBU medium. The addition of DBU was carried out to improve the catalyst performance in producing carboxylic acid products in the reaction of phenylacetylene carboxylation with CO2. HPLC analysis showed that the optimum results were obtained with the addition of 10 equivalents of DBU at 55 °C for 4 hours, with yields of 0.5382% for phenylpropiolic acid and 0.3459% for cinnamic acid, and phenylacetylene conversion reached 78.8452%.

Abstrak :
Gas rumah kaca seperti karbon dioksida merupakan gas yang melimpah di alam sehingga diperlukan cara untuk mengkonversi CO2. Namun, CO2 bersifat stabil secara termodinamika dan kinetika sehingga diperlukan bantuan logam bervalensi rendah contohnya Ni(0) atau Pd(0) untuk dapat bereaksi. Pada penelitian ini digunakan ZSM-5 hirarki terimpregnasi logam nikel sebagai katalis reaksi karboksilasi bertekanan antara fenilasetilena dengan karbon dioksida menjadi asam sinamat. ZSM-5 hirarki dianggap mampu menjadi penyangga katalis logam Ni dikarenakan ZSM-5 hirarki memiliki selektivitas dan transport massa yang baik. ZSM-5 Hirarki disintesis menggunakan metode double template yaitu TPAOH sebagai pengarah struktur MFI dan PDD-AM sebagai pengarah mesopori. Impregnasi logam nikel dilakukan menggunakan metode impregnasi basah dengan reduksi oleh aliran gas hidrogen. Karakterisasi material ZSM-5 hirarki dan Ni/ZSM-5 hirarki dilakukan dengan menggunakan XRD, FTIR, XRF, SEM-EDS dan SAA. Analisa XRD menunjukkan ZSM-5 telah berhasil disintesis. Analisa FTIR menunjukkan dekomposisi template melalui kalsinasi telah berhasil. Pencitraan SEM menunjukkan morfologi material dengan bentuk coffin like-shaped yang merupakan ciri khas ZSM-5. Hasil analisa EDS menunjukkan persen loading Ni dalam ZSM-5 sebesar 1,4 %. Sedangkan analisa XRF menunjukkan persen loading Ni dalam ZSM-5 sebesar 3,325 % yang mengindikasikan logam Ni telah masuk ke dalam pori ZSM-5. Analisa BET menunjukkan adanya hysteresis loop yang mengindikasikan adanya pori berukuran meso. Reaksi karboksilasi bertekanan fenilasetilena dilakukan dalam reaktor batch dengan variasi tekanan CO2 (1, 3, 5, 7 bar) dan suhu (85, 100, dan 125 C). Berdasarkan analisa terhadap campuran produk didapat tekanan CO2 optimum sebesar 3 bar dan suhu optimum pada 85 C. ...... Carbon dioxide is one of greenhouse gases which is abundant in nature, therefore efforts are needed to reduce its concentration through CO2 conversion. However, CO2 is thermodynamically and kinetically stable, so it needs low valent metals such as Ni (0) or Pd (0) to help CO2 to react. In this study, the hierarchical ZSM-5 impregnated nickel metal was used as a catalyst for pressurized carboxylation reactions between phenylacetylene and carbon dioxide to cinnamic acid. Hierarchical ZSM-5 is assumed capable for supporting Ni metal catalysts because it has good selectivity and mass transport. Hierarchical ZSM-5 was synthesized using the double template method with TPAOH as structure directing agent for MFI and PDD-AM as mesoporous directing agent. Impregnation of nickel was carried out using a wet impregnation method with reduction by the hydrogen gas flow. Material characterization of hierarchical ZSM-5 and Ni/ZSM-5 was carried out using XRD, FTIR, XRF, SEM-EDS and SAA. XRD analysis shows that ZSM-5 has been successfully synthesized. FTIR analysis showed that the template decomposition through calcination was successful. SEM imaging of the material shows a coffin-like morphology, which is a characteristic of the ZSM-5. The EDS analysis results shows 1.4% Ni in ZSM-5. While the XRF analysis shows 3.325 % Ni in ZSM-5 of which indicates that Ni has entered the ZSM-5 pores. BET analysis shows a hysteresis loop that indicates mesoporous. Pressurized carboxylation reaction of phenylacetylene were carried out in batch reactors with variations of CO2 pressure (1, 3, 5, 7 bar) and temperature (85, 100, and 125 125 C). Based on the analysis of products with HPLC, the optimal CO2 pressure was obtained at 3 bar and the optimal temperature at 85 C.

Abstrak :
ABSTRAK
Karbon dioksida (CO2) merupakan senyawa yang potensial digunakan sebagai sumber karbon dalam sintesis fine chemicals karena keberadaannya melimpah di alam, bersifat non toksik, ekonomis, dan termasuk ke dalam sumber yang dapat diperbaharui. Namun pemanfaatan CO2 secara luas masih terkendala karena sifatnya yang inert dan stabil. Oleh karena itu, keberadaan katalis sangat diperlukan dalam proses konversi CO2. Penelitian ini bertujuan untuk mensintesis Cu terimpregnasi pada karbon mesopori sebagai katalis karboksilasi fenilasetilena dengan CO2 menjadi asam karboksilat. Pembuatan karbon mesopori dilakukan dengan metode soft template menggunakan Pluronik F-127 sebagai pembentuk pori, formaldehida dan floroglusinol sebagai sumber karbon, dan HCl sebagai katalis asam. Material Cu/MC yang dihasilkan dikarakterisasi dengan FTIR, XRD, SAA, dan SEM-EDX. Analisis BET terhadap karbon mesopori menunjukkan bahwa material tersebut memiliki luas permukaan sebesar 405,8 m2/g dengan rata-rata pori sebesar 7,2 nm. Hasil analisa dengan XRD memperlihatkan puncak pada 2θ 36,62°; 43,47°; 50,63°; dan 74,19° yang mengindikasikan bahwa Cu telah berhasil terimpregnasi yang mewakili spesi Cu(0) dan Cu(I). Reaksi karboksilasi fenilasetilena dengan CO2 dilakukan dengan variasi suhu (25°C; 50°C; dan 75°C), variasi jumlah katalis (28,6; 57,2; dan 85,8 mg) dan variasi basa (Cs2CO3; K2CO3; dan Na2CO3). Hasil reaksi dianalisa dengan HPLC dan memperlihatkan %konversi terbaik terjadi pada suhu 75°C yaitu 41,32% dengan menggunakan Cs2CO3 sebagai basa, dan produk yang terbentuk diidentifikasi dengan FTIR dan LC-MS.

---

ABSTRACT
Carbon dioxide (CO2) is a compound that has the potential to be used as carbon source in the synthesis of fine chemicals because it is abundant in nature, non-toxic, inexpensive, and is included as a renewable source. However, utilization of CO2 is still constrained due to its inert and stable nature. Therefore, the presence of a catalyst is needed in CO2 conversion. This study aims to synthesize impregnated Cu on mesoporous carbon (Cu/MC) as a catalyst for phenylacetylene carboxylation reaction with CO2 into carboxylic acid. The synthesis of mesoporous carbon was performed via soft template method using Pluronic F-127 as a pore forming agen, formaldehyde and phloroglucinol as carbon sources, and HCl as an acid catalyst. The Cu/MC material produced was characterized by FTIR, SAA, XRD, and SEM-EDX. BET surface area analysis of mesoporous carbon showed that the material has a surface area of 405.8 m2/g with an average pore diameter of 7,2 nm. XRD pattern of Cu/MC showed some sharp peaks at 2θ of 36.62°; 43.47°; 50.63°; and 74.19° which indicates that Cu has been successfully impregnated in the form of Cu(0) and Cu(I). Phenylacetylene carboxylation reaction with CO2 was carried out by varying reaction temperatures (25, 50, and 75 °C), the amount of catalyst (28.6, 57.2, and 85.8 mg) and the type of base (Cs2CO3, K2CO3, and Na2CO3). The reaction mixtures were analyzed by HPLC and showed that highest phenylacetylene conversion of 41% was obtained for the reaction at 75°C using Cs2CO3 as a base. The product was further identified using FTIR and LCMS.