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"Karbon dioksida (CO2) merupakan gas rumah kaca utama yang mendorong perubahan iklim dan pengasaman laut. Walaupun demikian CO2 juga dapat menjadi sumber daya C1 yang berlimpah, tidak beracun, tidak mudah terbakar, dan dapat diperbaharui. Karena itu, konversi gas CO2 menjadi bahan kimia yang bernilai menjadi topik hangat untuk diteliti lebih dalam. Pada penelitian ini dilakukan penelitian terkait reaksi hidrokarboksilasi difenilasetilena dengan CO2 menggunakan katalis homogen utama yaitu Nickel(II) bis(acetylacetonate)bipyridine atau Ni(acac)2(bpy). Reaksi dilakukan dalam reaktor dengan kondisi yang bervariasi, yakni variasi banyaknya ligan bipiridin, variasi jenis sumber proton (metanol dan NaBH4), dan variasi jenis pelarut (DMF dan metanol). Reaksi dengan variasi kondisi optimal dilakukan variasi suhu (5℃, 27℃, 60℃) dan variasi waktu untuk mengetahui kondisi terbaik dari reaksi hidrokarboksilasi difenilasetilena. Selain itu, dianalisis terkait pengaruh preparasi katalis secara insitu dibandingkan dengan katalis hasil sintesis terhadap reaksi hidrokarboksilasi difenilasetilena. Produk dari reaksi hidrokarboksilasi yang diharapkan adalah asam α-fenilsinamat. Analisis HPLC terbaik ditunjukan oleh variasi banyaknya ligan dengan perbandingan Ni:bpy sebesar 1:1 dengan menggunakan pelarut DMF, sumber proton metanol, dan suhu reaksi 5℃ yang memberikan persen yield asam α-fenilsinamat sebesar 3,24%.

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Carbon dioxide (CO2) is a major greenhouse gas driving climate change and ocean acidification. However, CO2 can also be an abundant, non-toxic, non-flammable, and renewable C1 resource. Therefore, the conversion of CO2 gas into valuable chemicals is a hot topic for further research. In this study, a research was conducted on the hydrocarboxylation reaction of diphenylacetylene with CO2 using Nickel(II) bis(acetylacetonate)bipyridine (Ni(acac)2(bpy)) as main homogeneous catalyst. The reaction was carried out in a reactor with various conditions, namely variations in the number of bipyridine ligands, variations in the type of proton source (methanol and NaBH4), and variations in the type of solvent (DMF and methanol). The reaction with optimal conditions was carried out with variations in temperature (5℃, 27℃, 60℃) and time variations to determine the best condition of the hydrocarboxylation reaction. In addition, it was analyzed regarding the effect of in situ preparation of the catalyst compared to the synthesized catalyst on the diphenylacetylene hydrocarboxylation reaction. The expected product of the hydrocarboxylation reaction is α-phenylcinnamic acid. The best HPLC analysis was shown by variation in the number of bipyridine (Ni:bpy = 1:1) using DMF solvent, methanol as proton source, at reaction temperature of 5℃ which give an α-phenylcinnamic acid yield of 3,24%."

"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."

"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."

"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)

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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%."

"Karbondioksida merupakan gas rumah kaca yang menjadi salah satu faktor pemanasan global dan perubahan iklim secara drastis. Namun, di samping dampak negatif emisi gas CO2 secara alami maupun melalui hasil kegiatan antropogenik, CO2 dapat dimanfaatkan sebagai sumber C1 reaksi organik, salah satunya reaksi karboksilasi. Periodic Mesoporous Organosilica (PMO) merupakan material mesopori silika yang memiliki keunggulan, di antaranya memiliki ukuran pori cukup besar yang dapat memfasilitasi transfer massa dengan baik, luas permukaan besar yang memungkinkan banyak sisi katalitik, maupun integrasi dari spesi organik dan atom logam dalam kerangka PMO. Logam nikel merupakan logam yang secara luas digunakan dalam bidang katalisis, karena logam tersebut memiliki orbital d tidak terisi penuh, sehingga dapat membentuk ikatan kovalen koordinasi dan memudahkan proses pembentukan intermediet pada permukaan katalis. Pada penelitian ini, dilakukan sintesis PMO dengan prekursor 4,4’- bis(trietoksisilil)bifenil dan dilanjutkan dengan fungsionalisasi gugus amina melalui proses nitrasi dan aminasi. Selanjutnya, dilakukan imobilisasi kompleks Ni(acac)2 pada material Bph-PMO untuk digunakan sebagai katalis pada reaksi karboksilasi fenilasetilena dengan CO2. Analisis XRD menunjukkan bahwa fungsionalisasi gugus amina pada Bph-PMO tidak merubah komponen maupun struktur periodik pada Bph-PMO, begitu pula setelah nikel diimobilisasi pada Bph- PMO yang terfungsionalisasi gugus amina. Analisis FTIR Ni/NH2-Bph-PMO menunjukkan puncak serapan pada 1605 cm-1 yang mengindikasikan pembentukan ikatan C=N dari reaksi kondensasi Schiff antara gugus amina dengan C=O pada Ni(acac)2. Material Ni/NH2-Bph-PMO memiliki ukuran partikel rata-rata 420 nm, dengan pemuatan nikel 2,8% berdasarkan analisis SEM-EDX. Analisis TEM menunjukkan keberadaan struktur mesopori pada NH2-Bph-PMO. Ukuran diameter pori dan luas permukaan BET material Ni/NH2-Bph-PMO berturut-turut sebesar 3,16578 nm dan 490,742 m2/g. Uji katalitik material Ni/NH2-Bph-PMO pada karboksilasi fenilasetilena dengan CO2 dilakukan pada tiga variasi suhu, di mana kondisi optimum diperoleh pada suhu 25 °C, dengan konsentrasi produk fenil maleat 244,5899 ppm.

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ABSTRACTCarbon dioxide is a greenhouse gas that affecting global warming and produces climate change. However, aside from the negative effects of natural CO2 gas emissions and through anthropogenic activities, CO2 has been used as a source of C1 organic reactions, for example, carboxylation reaction. Periodic Mesoporous Organosilica (PMO) is a superior silica mesoporous material, which has a large pore to facilitate mass transfer, a large area that allows many catalytic sides, which also associated with organic species and metal atoms in PMO. This property supports PMO to be applied as a metal catalyst support. Nickel metal is a metal that is widely used in the catalysis field, because this metal has d orbitals and is not fully filled, so it can form covalent bonds and fasilitate process of making intermediates on the surface of the catalyst. In this study, PMO was synthesized with 4,4'-bis (triethoxysilyl) biphenyl precursor and continued with the functionalization of amine groups through nitration and amination process. Furthermore, immobilization of Ni(acac)2 complex was carried out on the Bph-PMO material to be used as a catalyst in the carboxylation reaction of phenylacetylene with CO2. Analysis of XRD shows that the functionalization of amine groups on Bph-PMO does not change the periodic structure of Bph-PMO, as well as after nickel immobilized on aminated Bph-PMO. Absorption peak at 1605 cm-1 of Ni/NH2- Bph-PMO revealed from FTIR analysis, indicating new C=N bond from Schiff condensation between amine group and C=O from Ni(acac)2. Ni/NH2-Bph-PMO material has an average particle size of 420 nm, with 2,8% nickel loading based on SEM-EDX analysis. Mesoporous structure of NH2-Bph-PMO has been proved by TEM analysis. The pore diameter size and BET surface area of Ni/NH2-Bph-PMO are 3,16578 nm and 490,742 m2/g, respectively. The catalytic test of Ni/NH2-Bph- PMO on phenylacetylene carboxylation with CO2 was carried out at three temperature variations, which shows that optimum condition was obtained at 25 °C, with a concentration of phenyl maleic product of 244,5899 ppm."

"Studi perbandingan katalis Cu/CeO2/Al2O3 dan Cu/ZnO/Al2O3 menjadi topik menarik untuk diteliti karena memiliki perbedaan konversi dan selektifitas terhadap produk alkohol. Katalis Cu/CeO2/Al2O3 dan Cu/ZnO/Al2O3 berhasil disintesis dan diuji kinerja katalisisnya dalam reaktor dengan perbandingan laju alir CO2:H2 sebesar 1:3 dengan suhu 250oC, 300oC dan 350oC. Penelitian ini bertujuan untuk melihat efektifitas dari kedua katalis dalam menghasilkan metanol dan ingin diketahui pengaruh pemberian beberapa variasi suhu. Hasil sintesis katalis dikarakterisasi menggunakan instrument SEM, XRD dan BET. Hasil reaksi hidrogenasi juga dikarakterisasi menggunakan VOC meter, IRGA dan GC-MS. Produk hasil hidrogenasi CO2 menggunakan katalis Cu-CeO2 menunjukkan konsentrasi senyawa organik secara beturut sebesar 4,7 ppm, 8,6 ppm dan 10,1 ppm dengan CO2 terkonversi sebesar 81,68%, 87,35% dan 90,14%, serta kromatogram GC-MS mengindikasikan senyawa metanol. Sedangkan dengan penggunaan katalis Cu-ZnO, didapatkan konsentrasi senyawa organik berturut sebesar 0,5 ppm, 1,0 ppm dan 2,4 ppm dengan CO2 terkonversi sebesar 81,46%, 81,58% dan 84,16%. Hasil tersebut menunjukan bahwa katalis Cu/CeO2/Al2O3 lebih efektif dalam menghidrogenasi CO2 menjadi metanol.

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Comparative studies of Cu/CeO2/Al2O3 and Cu/ZnO/Al2O3 catalysts is an interesting topic to research because of the differences of their conversion rates and selectivity to produce alcohol. Cu/CeO2/Al2O3 and Cu/ZnO/Al2O3 catalysts were successfully synthesized and the performances has been tested in a reactor with the ratio flow rate of CO2:H2 which is 1:3 temperatures of 250oC, 300oC dan 350oC. This study aimed to determine the abilities of both catalyst in producing metanol and to find the effect of several temperature variations. The characterizations of the synthesized catalysts were performed using SEM, XRD and BET instruments. The results of the hydrogenation reaction were also characterized using a VOC meter, IRGA and GC-MS. Products resulting from hydrogenation of CO2 using a Cu-CeO2 catalyst showed concentrations of organic compounds of 4.7 ppm, 8.6 ppm and 10.1 ppm with converted CO2 of 81.68%, 87.35% and 90.14% and GC-MS chromatograms indicates a methanol compound. Meanwhile, with the use of Cu-ZnO catalyst, the concentration of organic compounds was obtained, respectively, 0.5 ppm, 1.0 ppm and 2.4 ppm with converted CO2 of 81.46%, 81.58% and 84.16%. These results indicate that the Cu/CeO2/Al2O3 catalyst is more effective in hydrogenating CO2 into methanol."

"Konversi karbon dioksida menjadi senyawa lain saat ini telah dilakukan secara luas. Namun, konversi CO2 menjadi senyawa lain masih sulit karena CO2 bersifat inert dan stabil pada suhu tinggi. Jadi, dibutuhkan bantuan dari katalis logam bervalensi rendah seperti Ni (0) dan Pd (0). Dalam hal ini, ZSM-5 dari mineral alam disintesis menggunakan zeolit alam Bayat-Klaten dan kaolin Belitung sebagai sumber silika dan alumina. Bahan ini digunakan sebagai katalis untuk reaksi hidrogenasi CO2 (sabatier reaction. Hasil modifikasi Ni (0) pada material yang dihasilkan dikarakterisasi menggunakan FTIR, SEM-EDX, BET dan XRD. Reaksi yang berlangsung dilakukan dengan variasi massa katalis (0,02 gram dan 0,03 gram), suhu katalis (673 K, 773 K, dan 873 K) dan variasi perbandingan gas H2 dan CO2 (1: 3, 1: 4, dan 1:5) untuk melihat kemampuan konversi CO2 menjadi CH4. Proses reaksi hidrogenasi menggunakan flow quartz reactor dan dianalisis dengan Instrumen GC-TCD. Hasil modifikasi Ni/ZSM-5 dan H/ZSM-5 karakterisasi dengan FTIR, SEM-EDX, BET dan XRD. Konversi terbesar yang didapat dari katalis 10% Ni/ZSM-5 sintetik dengan konversi dan yield berturut-turut 60,55% dan 23% pada suhu 773 K.

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Conversion of carbon dioxide into other compounds nowadays have been widely carried out. However, the conversion is still difficult because CO2 is inert and stable at high temperatures. So it requires assistance from low-valence metal catalysts such as Ni (0) and Pd (0). In this work, ZSM-5 was synthesized using Bayat-Klaten natural zeolite and Belitung kaolin as its silica and alumina source. This material was used as support catalyst for CO2 hydrogenation reaction (sabatier reaction). The resulted for Ni (0) materials were characterized using FTIR, SEM-EDX, BET and XRD. The reaction was carried out with variations of catalyst mass (0.02 grams and 0.03 grams) temperature (673 K, 773 K, and 873 K) and mass flow ratio of CO2:H2 (1:3, 1: 4, and 1: 5). This reaction gave product only in the presence of Ni. The higher the Ni content the higher the conversion while the yield methane is unchanged. The highest conversion is shown by synthetic 10% Ni/ZSM-5 with conversion of 60.55% and yield of 23% at 773 K."

"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."

"Konversi karbon dioksida CO2 menjadi senyawa lain menjadi sangat menguntungkan karena jumlahnya di atmosfer yang melimpah, namun karbon dioksida CO2 memiliki termodinamik dan kinetik yang stabil sehingga diperlukan bantuan logam bervalensi rendah contohnya Ni 0 untuk dapat bereaksi. Pada penelitian ini digunakan ZSM-5 terimpregnasi logam nikel sebagai katalis reaksi karboksilasi asetilena dengan karbon dioksida menjadi asam akrilat. Hasil karakterisasi XRD menunjukan bahwa material ZSM-5 memiliki kristalinitas yang tinggi berhasil disintesis. Analisa menggunakan SEM menunjukan bahwa ZSM-5 memiliki morfologi bentuk coffin-like dan setelah diimpregnasi tidak mempengaruhi struktur morfologi kristal. Karakterisasi menggunakan BET ZSM-5 hirarki yang disintesis memiliki pori berukuran meso karena terbentuk hystheresis loop. Analisa menggunakan AAS menghasilkan loading logam nikel pada ZSM-5 mikropori sebesar 1,9 sedangkan ZSM-5 hirarki sebesar 2,1. Karakterisasi XPS menunjukan logam nikel pada ZSM-5 memiliki biloks nol 0. Pada reaksi karboksilasi asetilena dengan karbon dioksida dengan target produk asam akrilat, analisis HPLC tidak menunjukan adanya asam akrilat dalam reaksi. Namun, terdapat puncak lain pada waktu retensi 3,625 dimana pada material ZSM-5 hirarki didapatkan kondisi optimum pada suhu 80oC dengan suhu 12 jam dan menggunakan katalis Ni 0 /ZSM-5 mikropori didapatkan kondisi optimum pada suhu 40oC dan waktu 12 jam.

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Conversion of carbon dioxide CO2 into other compounds become very advantageous because of the abundance in the atmosphere, but carbon dioxide CO2 has thermodynamic and kinetic stable so it need low valent metal for example Ni 0 to react. In this studym ZSM 5 impregnated with nickel metal as catalyst of carboxylation reaction of acetylene with carbon dioxide to acrylic acid. XRD characterization results ZSM 5 material has high crytalinity successfully synthesized. Analysis using SEM obtain ZSM 5 has coffin like morphology and after impregnation doesnt affect the crystal morphology structure. Characterization using BET proves that ZSM 5 hierarchy has meso sized pore because of the hysthereses loop. Analyzing using AAS obtained that load of nickel metal on ZSM 5 micropore equal to 1,9 meanwhile ZSM 5 hierarchy equal to 2,1. The characterization of XPS show nickel metal on ZSM 5 has zero 0 oxidation. Carboxylation reaction of acetylene with carbon dioxide targeted acrylic acid product, HPLC analysis doesnt show the presence of acrylic acid in the reaction. However, there was another peak at retention time of 3,625 where in herarchical ZSM 5 material the optimum condition was obtained at temperature 80oC with 12 hours while using Ni 0 ZSM 5 micropore catalyst obtained 80oC with 12 hours. "

"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."