CO2 photocatalytic reduction is a carbon–neutral renewable energy technology. However, this technology is restricted by the low utilization of photocatalytic electrons. Therefore, to improve the separation efficiency of photogenerated carriers and enhance the performance of CO2 photocatalytic reduction. In this paper, g-C3N4/Pd composite with Schottky junction was synthesized by using g-C3N4, a two-dimensional material with unique interfacial effect, as the substrate material in combination with the co-catalyst Pd. The composite of Pd and g-C3N4 was tested to have a strong localized surface plasmon resonance effect (LSPR), which decreased the reaction barriers and improved the electron utilization. The combination of reduced graphene oxide (rGO) created a π–π conjugation effect at the g-C3N4 interface, which shortened the electron migration path and further improved the thermal electron transfer and utilization efficiency. The results show that the g-C3N4/ rGO/Pd (CRP) exhibits the best performance for photocatalytic reduction of CO2, with the yields of 13.57 μmol g− 1 and 2.73 μmol g− 1 for CO and CH4, respectively. Using the in situ infrared test to elucidate the intermediates and the mechanism of g-C3N4/rGO/Pd (CRP) photocatalytic CO2 reduction. This paper provides a new insight into the interface design of photocatalytic materials and the application of co-catalysts.

Electrochemical reduction of carbon dioxide to valuable chemicals is a promising way of storing renewable energy through electric-to-chemical energy conversion, while its large-scale application is in urgent need of cheap and high-performance catalysts. Herein, we invent a convenient method to synthesize N-doped porous carbon by ammonia etching the pyrolysis carbon of petroleum pitch. We found the ammonia etching treatment not only increase the pyridinic-N content, but also enlarge the specific surface area of the petroleum pitch-based porous carbon. As a cheap and easily available catalyst for carbon dioxide electroreduction, up to 82% of Faradaic efficiency towards carbon monoxide was obtained at − 0.9 V vs the reversible hydrogen electrode in 0.1 M KHCO3. After a long time electrocatalysis of more than 20 h, the Faradaic efficiency of carbon monoxide remains 80%, indicating the porous carbon as made have an ultra-high stability as catalyst for carbon dioxide reduction. Our work provides a new technology to economically prepare efficient electrocatalysts for carbon dioxide reduction.

Carbon-encapsulated Ni catalysts are synthesized by an electrical explosion of wires (EEW) method and applied for CO2 methanation. We find that the presence of carbon shell on Ni nanoparticles as catalyst can positively affect CO2 methanation reaction. Ni@5C that is produced under 5% CH4 partial pressure in Ar gas has highest conversions of 68 % at 350 oC and 70% at 400 oC, which are 73 and 75% of the thermodynamic equilibrium conversion, respectively. The catalyst of Ni@10C with thicker carbon layer shows much reduced activity. The EEW-produced Ni catalysts with low specific surface area outperform Ni catalysts with high surface area synthesized by solution-based precipitation methods. Our finding in this study shows the possibility of utilizing carbon-encapsulated metal catalysts for heterogeneous catalysis reaction including CO2 methanation. Furthermore, EEW, which is a highly promising method for massive production of metal nanoparticles, can be applied for various catalysis system, requiring scaled-up synthesis of catalysts.

본 연구는 폴리스타렌(PS) 수지의 유화공정 효율성 향상을 위해 저온열분해 회분식 반응기를 이용하여, 단일 PS 수지와 Co 및 Mo 촉매를 각각 첨가한 PS 수지를 반응온도(425, 450, 475℃), 반응 시간(20~80분, 15분 간격), 촉매 농도변화에 따른 PS수지의 액화생성물 전환율을 측정하였다. 최적의 열분해 조건은 반응온도 450℃, 반응시간 35분으로 판단되며, 전환된 액화생성물의 주요 성분은 GC/MS 분석결과 스타이렌 및 벤젠유도체가 대부분으로 나타났다. 생성물은 산업통상자원부에서 고시 한 증류성상 온도에 따라 가스, 가솔린, 등유, 경유, 중유로 분류하여 그 수율을 측정하였다. 그리고 45 0℃ 반응온도에서 촉매 사용에 따른 전환율은 Co 촉매 > Mo 촉매 > 무촉매 순이었으며, 생성물 중 가 스, 등유, 경유수율은 Mo 촉매, 가솔린은 무촉매, 중유는 Co 촉매에서 우수한 것으로 나타났다. Co 및 Mo 촉매 혼합 농도별 전환율 및 열분해 생성물 수율은 Co 촉매 100% 사용 시 가장 우수한 것으로 판 단된다.

Cu-Mn과 Cu-Zn 촉매를 침전제로 다르게 하거나, 금속의 몰비율, 소성온도를 다르게 하여 공침법으로 제조하였고 CO산화반응을 수행하여 혼합산화물 촉매에서 Cu, Mn과 Zn의 영향 및 소성온 도가 미치는 영향을 조사하였다. 촉매의 물리·화학적 특성을 알아보기 위하여 XRD, N2 흡착 및 SEM 의 분석을 수행하였다. Na2CO3로 침전시켜 270℃로 소성하여 제조한 2Cu-1Mn 산화물 촉매가 저온에 서 CO 산화반응 활성이 가장 좋았으며 2Cu-1Mn 산화물 촉매는 43 m2/g으로 가장 높은 비표면적과 촉매 활성을 나타내었다. XRD로 촉매의 결정구조를 분석하였을 때 Cu0.5Mn2.5O4의 결정구조를 갖는 촉 매는 낮은 활성을 보였다. 270℃에서 소성한 촉매가 좋은 활성을 나타냈으며 Pt 촉매와 비교하여도 저 온에서 CO산화반응이 더욱 우수함을 알 수 있었다.

Carbon-supported Pt catalyst systems containing defect adsorption sites on the anode of direct methanol fuel cells were investigated, to elucidate the mechanisms of H2 dissociation and carbon monoxide (CO) poisoning. Density functional theory calculations were carried out to determine the effect of defect sites located neighboring to or distant from the Pt catalyst on H2 and CO adsorption properties, based on electronic properties such as adsorption energy and electronic band gap. Interestingly, the presence of neighboring defect sites led to a reduction of H2 dissociation and CO poisoning due to atomic Pt filling the defect sites. At distant sites, H2 dissociation was active on Pt, but CO filled the defect sites to form carbon π-π bonds, thus enhancing the oxidation of the carbon surface. It should be noted that defect sites can cause CO poisoning, thereby deactivating the anode gradually.

본 연구는 폴리프로필렌(PP) 수지의 Co 및 Mo 촉매에 의한 반응시간과 농도변화에 따른 저온열분해 액화특성을 파악하고자 회분식 반응기를 이용하여 특정 온도(425, 450, 475℃)에서의 전환율을 측정하였다. 열분해 시간은 20~80분으로 설정하였고 생성물은 산업통상자원부에서 고시한 증류성상 온도에 따라 가스, 가솔린, 등유, 경유, 중유로 분류하였다. 그리고 450℃ 반응온도에서 촉매 사용에 따른 전환율은 모든 반응시간에 있어 Mo 촉매 > Co 촉매 > 무촉매 순이었다. Co 및 Mo 촉매 농도별 PP 전환율 및 열분해 생성물 수율은 Co:Mo=50:50 혼합시 가장 우수한 것으로 나타났다.

The electrocatalytic characteristics of oxygen reduction reaction of the PtxM(1-x) (M = Co, Cu, Ni) supported on multi-walled carbon nanotubes (MWNTs) have been evaluated in a Polymer Electrolyte Membrane Fuel Cell (PEMFC). The PtxM(1-x)/MWNTs catalysts with a Pt : M atomic ratio of about 3 : 1 were synthesized and applied to the cathode of PEMFC. The crystalline structure and morphology images of the PtxM(1-x) particles were characterized by X-ray diffraction and transmission electron microscopy, respectively. The results showed that the crystalline structure of the Pt alloy particles in Pt/MWNTs and PtxM(1-x)/MWNTs catalysts are seen as FCC, and synthesized PtxM(1-x) crystals have lattice parameters smaller than the pure Pt crystal. According to the electrochemical surface area (ESA) calculated with cyclic voltammetry analysis, Pt0.77Co0.23/MWNTs catalyst has higher ESA than the other catalysts. The evaluation of a unit cell test using Pt/MWNTs or PtxM(1-x)/MWNTs as the cathode catalysts demonstrated higher cell performance than did a commercial Pt/C catalyst. Among the MWNTs-supported Pt and PtxM(1-x) (M = Co, Cu, Ni) catalysts, the Pt0.77Co0.23/MWNTs shows the highest performance with the cathode catalyst of PEMFC because they had the largest ESA.

CuxFe3-xO4 catalyst and ZnxFe3-xO4 catalyst were synthesized by the air oxidation method with various C(II) and Zn(II) weights. Activated catalysts decomposed carbon dioxide to carbon at 350℃, 380℃, 410℃ and 440℃. The value of carbon dioxide decomposition rate for Cu0.003Fe2.997O4 and Zn0.003Fe2.997O4 catslysts than was better catalysts. The decomposed rate of the catalysts is about 85%~90%. The reaction rate constant(4.00 psi1-α/min) and activation energy(2.62 kcal/mole) of Cu0.003Fe2.997O4 catalyst are better than Zn0.003Fe2.997O4

The Cuo-Magnetite and ZnO-Magnetite catalysts with various of Cuo and ZnO mole% for Carbon Dioxide decomposed reaction synthesized. The catalysts were reduced by H2 at 350℃ for 3 hours. The temperature was obtained by TGA and DSC experiments. The structures of catalysts were confirmed by X-ray diffraction experiment. The surface area of catalysts is 15~27 m2/g. The results of Carbon Dioxide decomposed ability was better H2-reduced magnetite catalysts with 0.03 mole% CuO and 0.03 mole% ZnO than others catalysts. After Carbon Dioxide decomposed reaction, catalysts were reacted H2 and created only methane.

TiO2- and SiO2-supported Co3O4, Pt and Co3O4-Pt catalysts have been studied for CO and C3H8 oxidations at temperatures less than 250℃ which is a lower limit of light-off temperatures to oxidize them during emission test cycles of gasoline-fueled automotives with TWCs (three-way catalytic converters) consisting mainly of Pt, Pd and Rh. All the catalysts after appropriate activation such as calcination at 350℃ and reduction at 400℃ exhibited significant dependence on both their preparation techniques and supports upon CO oxidation at chosen temperatures. A Pt/TiO2 catalyst prepared by using an ion-exchange method (IE) has much better activity for such CO oxidation because of smaller Pt nanoparticles, compared to a supported Pt obtained via an incipient wetness (IW). Supported Co3O4-only catalysts are very active for CO oxidation even at 100℃, but the use of TiO2 as a support and the IW technique give the best performances. These effects on supports and preparation methods were indicated for Co3O4-Pt catalysts. Based on activity profiles of CO oxidation at 100℃ over a physical mixture of supported Pt and Co3O4 after activation under different conditions, and typical light-off temperatures of CO and unburned hydrocarbons in common TWCs as tested for C3H8 oxidation at 250℃ with a Pt-exchanged SiO2 catalyst, this study may offer an useful approach to substitute Co3O4 for a part of platinum group metals, particularly Pt, thereby lowering the usage of the precious metals.

The formation of ConTiOn+₂ compounds, i.e., CoTiO₃ and Co2TiO₄, in a 5 wt% CoOx/TiO2 catalyst after calcination at different temperatures has been characterized via scanning electron microscopy (SEM), Raman and X-ray photoelectron spectroscopy (XPS) measurements to verify our earlier model associated with Co3O4 nanoparticles present in the catalyst, and laboratory-synthesized ConTiOn+₂ chemicals have been employed to directly measure their activity profiles for CO oxidation at 100˚C. SEM measurements with the synthetic CoTiO₃ and Co2TiO₄ gave the respective tetragonal and rhombohedral morphology structures, in good agreement with the earlier XRD results. Weak Raman peaks at 239, 267 and 336 cm-1 appeared on 5 wt% CoOx/TiO₂ after calcination at 570oC but not on the catalyst calcined at 450˚C, and these peaks were observed for the ConTiOn+₂ compounds, particularly CoTiO3. All samples of the two cobalt titanate possessed O 1s XPS spectra comprised of strong peaks at 530.0±0.1 eV with a shoulder at a 532.2-eV binding energy. The O 1s structure at binding energies near 530.0 eV was shown for a sample of 5 wt% CoOx/TiO₂, irrespective to calcination temperature. The noticeable difference between the catalyst calcined at 450 and 570˚C is the 532.2 eV shoulder which was indicative of the formation of the ConTiOn+₂ compounds in the catalyst. No long-life activity maintenance of the synthetic ConTiOn+₂ compounds for CO oxidation at 100˚C was a good vehicle to strongly support the reason why the supported CoOx catalyst after calcination at 570˚C had been practically inactive for the oxidation reaction in our previous study; consequently, the earlier proposed model for the Co₃O₄ nanoparticles existing with the catalyst following calcination at different temperatures is very consistent with the characterization results and activity measurements with the cobalt titanates.