In present study, Cu–Ni/AC and V-doped Cu–Ni/AC were prepared using an impregnation and co-impregnation methods respectively for dimethyl carbonation (DMC) formation from CH₃OH carbonation at various temperatures (110, 170, and 220°C) and CO₂/N₂ volumetric flow ratios (1/4, 1/7, and 1/9). Effects of vanadium addition on Cu–Ni/AC intrinsic properties and catalytic performances were investigated. Decrease of Cu–Ni/AC surface acidity with vanadium addition was found with NH₃–temperature programmed desorption (NH₃–TPD) at 25–450°C. Furthermore, the valence shifts of metallic atoms in catalysts were found by X–ray absorption near–edge structure/extended X–ray absorption fine structure (XANES/EXAFS). Optimal reaction conditions (170°C and CO₂/N₂ = 1/7) with the highest CH₃OH conversion (8.1%), DMC selectivity (93.2%), and DMC yield (7.5%) were confirmed in a fixed-bed column reactor. Linear regressions of the pseudo-first-order, pseudo-second-order, and third-order models referred that the largest CH₃OH consumption rate constant (15.56 × 10⁻³ 1/min, 9.29 L/mol-min), turnover number (TON = 17.89), and turnover frequency (TOF = 3.73 × 10⁻² 1/min) of DMC formation were acquired with V-doped Cu–Ni/AC at optimal reaction conditions. A reaction mechanism over Cu–Ni/AC or V-doped Cu–Ni/AC active sites was proposed.

在本研究中，分别使用浸渍和共浸渍方法制备了Cu-Ni / AC和V掺杂的Cu-Ni / AC，用于在各种温度下（110、170和110℃ ）从CH ₃ OH碳酸化生成二甲基碳酸化（DMC）。220°C）和CO ₂ / N ₂体积流量比（1 / 4、1 / 7和1/9）。研究了钒添加对Cu-Ni / AC固有性质和催化性能的影响。在25–450的NH ₃ –程序升温脱附（NH ₃ –TPD）下，发现添加钒会降低Cu–Ni / AC表面酸度℃。此外，通过X射线吸收近边缘结构/扩展的X射线吸收精细结构（XANES / EXAFS）发现了催化剂中金属原子的化合价变化。最佳反应条件（170在固定床塔式反应器中，确认到具有 最高CH ₃ OH转化率（8.1％），DMC选择性（93.2％）和DMC产率（7.5％）的°C和CO ₂ / N ₂ = 1/7）。拟一阶，拟二阶和三阶模型的线性回归表明，最大的CH ₃ OH消耗速率常数（15.56×10 ^-3 1 / min，9.29 L / mol-min），周转率在最佳反应条件下，用V掺杂的Cu-Ni / AC可获得DMC的DMC形成数（TON = 17.89）和周转频率（TOF = 3.73×10 ^-2 1 / min）。提出了在Cu-Ni / AC或V掺杂的Cu-Ni / AC活性位上的反应机理。