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"Kenaikan sejumlah besar CO₂ mengakibatkan konsentrasi CO₂ semakin meningkat di atmosfer secara terus-menerus yang menyebabkan terjadinya perubahan iklim. Pengembangan reaksi katalitik terbarukan diperlukan untuk mentransformasi CO₂ menjadi produk yang lebih bermanfaat. Pada penelitian ini, telah dilakukan uji reaksi karboksilasi fenilasetilena dengan CO₂ menggunakan katalis Ni(acac)₂, NiCl₂ dan Ni(DBU)₂ yang terimpregnasi pada penyangga karbon mesopori. Material karbon mesopori, Ni(acac)₂/ MC, NiCl₂/ MC dan Ni(DBU)₂/ MC dikarakterisasi dengan FT-IR, XRD, SAA dan SEM-EDS. Karbon mesopori telah berhasil disintesis menggunakan metode soft template dibuktikan dengan hasil  analisa XRD yang menunjukkan pola difraksi secara khas pada material karbon pada 25,68^o dan 43,26^o dengan indeks Miller (002) dan (100). Proses impregnasi  pada Ni(acac)₂, NiCl₂ dan Ni(DBU)₂  pada penyangga karbon mesopori telah berhasil ditunjukkan dengan analisa FT-IR dimana pada spektrum Ni(acac)₂/ MC, NiCl₂/ MC dan Ni(DBU)₂/ MC menghasilkan spektrum yang sama dengan MC dikarenakan senyawa terimpregnasi telah masuk ke dalam pori sehingga mengakibatkan tidak terdeteksinya gugus fungsi yang ada pada senyawa-senyawa tersebut. Hasil karakterisasi SAA menunjukkan bahwa ketiga katalis heterogen termasuk ke dalam material mesopori. Radius pori yang diperoleh pada ketiga senyawa yaitu  Ni(acac)₂/ MC sebesar 3,288 nm, NiCl₂/ MC sebesar 4,799 nm, dan Ni(DBU)₂/ MC sebesar 4,763 nm. Uji daya adsorpsi dan uji reaksi karboksilasi fenilasetilena dengan CO₂ dengan katalis heterogen Ni(acac)₂/ MC, NiCl₂/ MC dan Ni(DBU)₂/ MC telah dilakukan dan membuktikan bahwa katalis Ni(acac)2/ MC memiliki daya adsorpsi lebih baik dan menghasilkan produk fenil maleat lebih banyak dibanding dengan katalis NiCl₂/ MC dan Ni(DBU)₂/ MC.

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The continuous increase of CO₂ concentrations in the atmosphere for decades has influenced the global climate change. The development of renewable catalytic reactions is needed to transform CO₂ into more useful products. In this research, phenylacetylene carboxylation reaction with CO₂ was tested using catalysts Ni(acac)₂, NiCl₂ and Ni(DBU)₂ which were impregnated on the mesoporous carbon support. Mesoporous carbon materials, Ni(acac)₂ / MC, NiCl₂ / MC , and Ni(DBU)₂ / MC are characterized by FT-IR, XRD, SAA and SEM-EDS. Mesoporous carbon was successfully synthesized using soft template method which showed typical diffraction patterns of carbon materials which were 25.68^o and 43.26^o with the Miller index of (002) and (100), respectively. The impregnation process in Ni(acac)₂, NiCl₂ and Ni(DBU)₂ in mesoporous carbon support has been successfully proven by FT-IR analysis in which Ni(acac)₂ / MC, NiCl₂ / MC, and Ni(DBU)₂ / MC have similiar IR-spectrum to MC IR-spectrum because the compounds have been substituted into the pore so that no functional groups were detected in the samples. The results of the SAA characterization showed that the three heterogeneous catalysts belong to compounds that have meso-sized pores. The pore radius obtained in the three materials were 3,288 nm for Ni(acac)₂ / MC, 4,799 nm for NiCl₂ / MC, and 4,763 nm for Ni(DBU)₂ / MC. Adsorption test and phenylacetylene carboxylation reaction test with CO₂ with heterogeneous catalyst Ni(acac)₂ / MC, NiCl₂ / MC and Ni(DBU)₂ / MC have been carried out and proved the Ni(acac)₂ / MC catalyst had better adsorption performance and produced more phenyl maleate product compared to NiCl₂ / MC and Ni(DBU)₂ / MC catalysts."

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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.

 

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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.

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"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.

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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."

"Karbon dioksida (CO2) salah satu komponen utama gas rumah kaca yang merupakan penyumbang total terbesar terhadap perubahan iklim. Oleh karena itu, perlu dilakukan pengurangan emisi gas CO2, baik dengan menyimpan maupun memanfaatkan CO2 sebagai sumber penghasil bahan kimia yang lebih bermanfaat melalui reaksi katalitik heterogen. Dalam penelitian ini, Ni(0) yang disangga pada karbon mesopori (MC) digunakan sebagai katalis untuk mengonversi CO2 menjadi gas metana dalam reaksi Sabatier. Karbon mesopori berhasil disintesis dengan metode cetakan lunak menggunakan phloroglucinol, Pluronic F127, dan formaldehida sebagai prekursor. Karbon mesopori hasil sintesis dikarakterisasi menggunakan instrumen FTIR, XRD, SEM-EDS, TEM, SAA, dan Raman kemudian dimodifikasi menggunakan nanopartikel Ni(0) dari prekursor Ni(NO3)2.6H2O dan Ni(acac)2 dalam jumlah tertentu. Katalis Ni(0)/MC yang disintesis kemudian diberi label sebagai Ni/MC(5)(Ni(NO3)2) dan Ni/MC(30)(Ni(NO3)2) untuk 5% dan 30% Ni(0) dari Ni(NO3)2.6H2O dan Ni/MC(30)(Ni(acac)2) untuk 30% Ni(0) dari Ni(acac)2. Katalis Ni(0)/MC dikarakterisasi menggunakan instrumen FTIR, XRD, SEM-EDS, TEM, SAA, dan Raman. MC dan Ni(0)/MC hasil sintesis digunakan sebagai katalis untuk reaksi konversi CO2 menjadi CH4 menggunakan tubular furnace pada T = 873 K selama 9 menit. Produk hasil reaksi diukur menggunakan kromatografi gas dengan detektor TCD. %yield produk dari hasil reaksi adalah 0%; 1,33%; 1,63%; dan 1,9% untuk MC, Ni/MC(5)(Ni(NO3)2), Ni/MC(30)(Ni(NO3)2), dan Ni/MC(30)(Ni(acac)2). Hasil penelitian menunjukkan bahwa %yield setelah percobaan ke-2, ke-3, dan ke-4 secara bertahap menurun. Hasil ini menunjukkan bahwa nanopartikel Ni(0) memiliki peran penting untuk mengaktifkan CO2 serta penurunan kapasitas reaksi seiring dengan pengujian berkala dapat disebabkan oleh transformasi Ni(0) menjadi nanopartikel Ni(II).

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Carbon dioxide (CO2), a major component of greenhouse gases, is the largest total contributor to the climate change. Therefore, it is necessary to reduce the CO2 gas emissions, either by storing or utilizing CO2 as a source to produce value-added chemicals through heterogenous catalytic reactions. In this work, Ni(0) supported on mesoporous carbon (MC) was used as catalyst to convert CO2 to methane gas in Sabatier reaction. Mesoporous carbon was successfully synthesized by a soft template method using phloroglucinol, Pluronic F127 and formaldehyde as precursors. The as-synthesized mesoporous carbon was characterized using FTIR, XRD, SEM-EDS, TEM, SAA, and Raman instruments and then modified with Ni(0) nanoparticles using certained amount of Ni(NO3)2.6H2O or Ni(acac)2 as precursor. The prepared Ni(0)/MCs then were label as Ni/MC(5)(Ni(NO3)2) and Ni/MC(30)(Ni(NO3)2) for 5% and 30% Ni(0) from Ni(NO3)2.6H2O, and Ni/MC(30)(Ni(acac)2) for 30% Ni(0) from Ni(acac)2, respectively. The Ni(0)/MC catalysts was characterized using FTIR, XRD, SEM-EDS, TEM, SAA, and Raman instruments. Both as-synthesized MC and Ni(0)/MC then used as the catalysts for CO2 conversion reaction to CH4 using tubular furnace at T = 873 K for 9 minutes. The product reaction was measured using gas-chromatography with thermal conductivity detector. The % yield of products from reaction are 0%; 1.33%; 1.62%; and 1.9% for MC, Ni/MC(5)(Ni(NO3)2), Ni/MC(30)(Ni(NO3)2) and Ni/MC(30)(Ni(acac)2) respectively. The CO2 conversion reaction capacity was also conducted using Ni/MC(30)(Ni(acac)2) to evaluate the catalyst performance. The results shows that the % yield of the reaction after 2nd, 3rd, and 4th attempt were gradually decreased. These results shows that Ni(0) nanoparticles have an important role for activating the CO2 and the decreases of the reaction capacity along periodic test may be caused by the transformation of Ni(0) into Ni(II) nanoparticles."

"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 %.

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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%."

"Reaksi karboksilasi fenilasetilena dengan CO₂ dilakukan dengan menggunakan katalis Ni-Ga dan Ni-Ga termodifikasi timah (Sn) yang disangga oleh karbon mesopori (MC). MC disintesis dengan metode soft template dan dianalisis dengan TGA diperoleh kestabilan termal hingga 850 °C. Katalis dikarakterisasi dengan FTIR, XRD, Raman, SEM, TEM, dan BET. Hasil XRD menunjukkan puncak pada 24,47°; 32,73°; 43,83°; 50,96°; 74,32°yang merupakan difraksi Ni₅Ga₃ dan partikel Sn(0) pada penyangga MC. Penambahan Sn diketahui tidak mengubah kestabilan katalis Ni₅Ga₃/MC yang dikonfirmasi melalui FTIR dan Raman. Hasil SEM dan TEM juga menunjukkan partikel Ni-Ga-Sn tersebar merata pada permukaan karbon mesopori. BET menunjukkan katalis termasuk dalam ukuran mesopori 2-50 nm. Uji aktivitas katalitik berdasarkan analisa HPLC menunjukkan hasil optimum diperoleh dengan menggunakan katalis Ni₅Ga₃Sn₀‚₅/MC pada suhu 50°C selama 8 jam. Sedangkan berdasarkan LC-MS, diketahui terbentuk produk asam sinamat dan asam fenil propiolat dengan yield masing-masing 2,14% dan 3,04% dengan konversi fenilasetilena mencapai 93,06%.

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The carboxylation reaction of phenylacetylene with CO2 was carried out using Ni-Ga and Ni-Ga-modified tin catalysts supported by mesoporous carbon (MC). MC was synthesized using the soft template method and analyzed using TGA and obtained thermal stability up to 850 0C. To determine the modification effect of Sn addition, catalysts were synthesized with variations of Ni5Ga3/MC, Ni5Ga3Sn0.1/MC, Ni5Ga3Sn0.3/MC, Ni5Ga3Sn0.5/MC, Ni5Ga3Sn0.7/MC, Ni5Ga3Sn0.9/MC. The catalysts were characterized by FTIR, XRD, Raman, SEM, TEM, and BET. XRD results show peaks at 24.47o; 32.73 o; 43.83o; 50.96 o; and 74.32o which is the diffraction of the Ni5Ga3 phase and Sn (0) particles on the MC support. The addition of Sn metal is known not to change the stability of the Ni5Ga3/MC catalyst which was confirmed through FTIR and Raman spectra. SEM and TEM results also show that Ni-Ga-Sn particles are evenly distributed on the mesoporous carbon surface with a spherical shape. BET-SAA shows the pore diameter size of the materials Ni5Ga3/MC, Ni5Ga3Sn0.1/MC, Ni5Ga3Sn0.3/MC, Ni5Ga3Sn0.5/MC, Ni5Ga3Sn0.7/MC, Ni5Ga3Sn0.9/MC respectively, are 6.24 nm; 6.22nm; 7.22nm; 6.24 nm, 7.22 nm, and 10.46 nm which are included in the mesopore size of 2-50 nm. The catalytic activity test was carried out through the carboxylation reaction of phenylacetylene with CO2 using variations of catalyst, time and temperature. HPLC analysis showed that optimum results were obtained using the Ni5Ga3Sn0.5/MC catalyst at a temperature of 500C for 8 hours. Meanwhile, based on LC-MS, it is known that cinnamic acid and phenyl propiolic acid products were formed with yields of 2.14% and 3.04% respectively with 93.06% phenylacetylene conversion."

"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."

"ABSTRAKKarbon 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.

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ABSTRACTCarbon 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 stillconstrained 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."

"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.

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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."

"ABSTRACTKarbon dioksida (CO2) adalah gas rumah kaca utama yang menyebabkan pemanasan global dan perubahan iklim. Karena jumlahnya yang melimpah, CO2 dapat dijadikan sebagai sumber C1 terbarukan untuk sintesis bahan kimia yang berguna. Dalam penelitian ini, telah 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. 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 dengan kondisi reaksi yang bervariasi, yakni variasi jenis pelarut (DMF dan Toluene), variasi tekanan (1 atm, 3 atm, 5 atm), variasi suhu (85oC, 100oC, 125oC). Produk reaksi karboksilasi ini yang diharapkan merupakan asamsinamat yang kemudian dianalisis dengan menggunakan HPLC untuk menentukan %yield dan %konversi.

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ABSTRACTCarbon dioxide (CO2) is the main greenhouse gas that causes global warming and climate change. Due to its abundance, CO2 can be used as a renewable C1 source for the synthesis of useful chemicals. In this research, carboxylation reaction of phenylacetylene with CO2 has been carried out using nickel impregnated in 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 impregnating nickel into mesoporous carbon (Ni@MC). Ni@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 (85oC, 100oC, 125oC), solvent (DMF and Toluene), and pressure (1 atm, 3 atm, 5 atm). The result of carboxylation reactions which is expected to be cinnamic acid, were analyzed by HPLC and LC MS to determine yield and conversion."