Electrocatalytic reduction of CO_(2)is one of the most attractive approaches for converting CO_(2)into valuable chemical feedstocks and fuels.This work reports a catalyst comprising graphdiyne-decorated bismuth subcar...Electrocatalytic reduction of CO_(2)is one of the most attractive approaches for converting CO_(2)into valuable chemical feedstocks and fuels.This work reports a catalyst comprising graphdiyne-decorated bismuth subcarbonate(denoted as BOC@GDY)for efficient electroreduction of CO_(2)to formate.The BOC@GDY shows a stable current density of 200 mA cm^(-2)at–1.1 V in a flow cell configuration,with a faradaic efficiency of 93.5%for formate.Experimental results show that the synergistic effect in BOC@GDY is beneficial for the CO_(2)adsorption affinity,the reaction kinetics and the selectivity for formate.In addition,in-situ X-ray absorption and Raman spectroscopy indicate that the electron-rich GDY could facilitate the reduction from Bi(Ⅲ)to Bi(0),thus leading to more active sites.We also demonstrate that the promoting effect of GDY in CO_(2)electroreduction can be further extended to other metal catalysts.To the best of our knowledge,such general promoting functions of GDY for CO_(2)electroreduction have not been documented thus far.展开更多
Bismuth-based materials(e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO_(2) to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismu...Bismuth-based materials(e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO_(2) to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismuth oxides and subcarbonate encounter stability issues. This work is designated to exemplify that the operando synthesis can be an effective means to enhance the stability of electrocatalysts under operando CO_(2)RR conditions. A synthetic approach is developed to electrochemically convert Bi^(O)Cl into Cl-containing subcarbonate(Bi_(2)O_(2)(CO_(3))_(x)Cl_(y)) under operando CO_(2)RR conditions. The systematic operando spectroscopic studies depict that BiOCl is converted to Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) via a cathodic potential-promoted anion-exchange process. The operando synthesizedBi_(2)O_(2)(CO_(3))_(x)Cl_(y) can tolerate-1.0 V versus RHE, while for the wet-chemistry synthesized pure Bi_(2)O_(2)CO_(3),the formation of metallic Bio occurs at-0.6 V versus RHE. At-0.8 V versus RHE, Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) can readily attain a FEHCOO-of 97.9%,much higher than that of the pure Bi_(2)O_(2)CO_(3)(81.3%). DFT calculations indicate that differing from the pure Bi_(2)O_(2)CO_(3)-catalyzed CO_(2)RR, where formate is formed via a *OCHO intermediate step that requires a high energy input energy of 2.69 eV to proceed, the formation of H COO-over Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) has proceeded via a *COOH intermediate step that only requires low energy input of 2.56 eV.展开更多
Hierarchical microspheres of a graphene oxide（GO） coupled to N‐doped（BiO）2CO3 composite（N‐BOC‐GO） was synthesized by a simple hydrothermal approach. The N‐BOC‐GO composite gave enhancement in photocatalytic...Hierarchical microspheres of a graphene oxide（GO） coupled to N‐doped（BiO）2CO3 composite（N‐BOC‐GO） was synthesized by a simple hydrothermal approach. The N‐BOC‐GO composite gave enhancement in photocatalytic activity compared to the pure BOC and N‐BOC samples. With 1.0wt% GO, 62% NO removal was obtained with N‐BOC‐GO. The factors enhancing the photocatalytic performance were the high electron‐withdrawing ability and high conductivity of GO and improved visible light‐harvesting ability of N‐BOC‐GO with a 3D hierarchical architecture due to the surface scattering and reflecting（SSR） effect. An effective charge transfer from N‐BOC to GO was demonstrated by the much weakened photoluminescene intensity of the N‐BOC‐GO composite. This work highlights the potential application of GO‐based photocatalysts in air purification.展开更多
In order to solve the problems of environment pollution and high cost in traditional process of bismuth subcarbonate preparation, a new process using ball-milling transformation method from NH4HCO3 and Bi2O3 was propo...In order to solve the problems of environment pollution and high cost in traditional process of bismuth subcarbonate preparation, a new process using ball-milling transformation method from NH4HCO3 and Bi2O3 was proposed. Additionally, the kinetics of bismuth subcarbonate preparation was studied. Effects of reaction temperature, particle size of bismuth oxide, solid-to-liquid ratio and concentrations of ammonium bicarbonate on the conversion rate of bismuth oxide were studied. The results indicate that the conversion rate of bismuth oxide significantly increased under the conditions of higher temperature, smaller particle size, higher concentration of ammonium bicarbonate and smaller solid-to-liquid ratio. The XRD and ICP-AES analyses show that the purity of product is high. The reaction kinetics with activation energy of 9.783 kJ/mol was analyzed by shrinking core model, and the whole transformation process is controlled by solid product layer diffusion. A semi-empirical kinetics equation was obtained to describe the conversion process.展开更多
基金the National Key R&D Program of China(2017YFA0700104)the National Natural Science Foundation of China(21790052,21805207,and 21931007)+1 种基金111 Project of China(D17003)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(2018KJ129)。
文摘Electrocatalytic reduction of CO_(2)is one of the most attractive approaches for converting CO_(2)into valuable chemical feedstocks and fuels.This work reports a catalyst comprising graphdiyne-decorated bismuth subcarbonate(denoted as BOC@GDY)for efficient electroreduction of CO_(2)to formate.The BOC@GDY shows a stable current density of 200 mA cm^(-2)at–1.1 V in a flow cell configuration,with a faradaic efficiency of 93.5%for formate.Experimental results show that the synergistic effect in BOC@GDY is beneficial for the CO_(2)adsorption affinity,the reaction kinetics and the selectivity for formate.In addition,in-situ X-ray absorption and Raman spectroscopy indicate that the electron-rich GDY could facilitate the reduction from Bi(Ⅲ)to Bi(0),thus leading to more active sites.We also demonstrate that the promoting effect of GDY in CO_(2)electroreduction can be further extended to other metal catalysts.To the best of our knowledge,such general promoting functions of GDY for CO_(2)electroreduction have not been documented thus far.
基金financially supported by Australian Research Council Discovery Project(DP200100965)。
文摘Bismuth-based materials(e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO_(2) to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismuth oxides and subcarbonate encounter stability issues. This work is designated to exemplify that the operando synthesis can be an effective means to enhance the stability of electrocatalysts under operando CO_(2)RR conditions. A synthetic approach is developed to electrochemically convert Bi^(O)Cl into Cl-containing subcarbonate(Bi_(2)O_(2)(CO_(3))_(x)Cl_(y)) under operando CO_(2)RR conditions. The systematic operando spectroscopic studies depict that BiOCl is converted to Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) via a cathodic potential-promoted anion-exchange process. The operando synthesizedBi_(2)O_(2)(CO_(3))_(x)Cl_(y) can tolerate-1.0 V versus RHE, while for the wet-chemistry synthesized pure Bi_(2)O_(2)CO_(3),the formation of metallic Bio occurs at-0.6 V versus RHE. At-0.8 V versus RHE, Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) can readily attain a FEHCOO-of 97.9%,much higher than that of the pure Bi_(2)O_(2)CO_(3)(81.3%). DFT calculations indicate that differing from the pure Bi_(2)O_(2)CO_(3)-catalyzed CO_(2)RR, where formate is formed via a *OCHO intermediate step that requires a high energy input energy of 2.69 eV to proceed, the formation of H COO-over Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) has proceeded via a *COOH intermediate step that only requires low energy input of 2.56 eV.
基金supported by the National Natural Science Foundation of China(21277097)the Key Projects in the National Science&Technology Pillar Program during the 12th Five-Year Plan Period(2012BAJ21B01)~~
文摘Hierarchical microspheres of a graphene oxide（GO） coupled to N‐doped（BiO）2CO3 composite（N‐BOC‐GO） was synthesized by a simple hydrothermal approach. The N‐BOC‐GO composite gave enhancement in photocatalytic activity compared to the pure BOC and N‐BOC samples. With 1.0wt% GO, 62% NO removal was obtained with N‐BOC‐GO. The factors enhancing the photocatalytic performance were the high electron‐withdrawing ability and high conductivity of GO and improved visible light‐harvesting ability of N‐BOC‐GO with a 3D hierarchical architecture due to the surface scattering and reflecting（SSR） effect. An effective charge transfer from N‐BOC to GO was demonstrated by the much weakened photoluminescene intensity of the N‐BOC‐GO composite. This work highlights the potential application of GO‐based photocatalysts in air purification.
基金Project(50774099)supported by the National Natural Science Foundation of China
文摘In order to solve the problems of environment pollution and high cost in traditional process of bismuth subcarbonate preparation, a new process using ball-milling transformation method from NH4HCO3 and Bi2O3 was proposed. Additionally, the kinetics of bismuth subcarbonate preparation was studied. Effects of reaction temperature, particle size of bismuth oxide, solid-to-liquid ratio and concentrations of ammonium bicarbonate on the conversion rate of bismuth oxide were studied. The results indicate that the conversion rate of bismuth oxide significantly increased under the conditions of higher temperature, smaller particle size, higher concentration of ammonium bicarbonate and smaller solid-to-liquid ratio. The XRD and ICP-AES analyses show that the purity of product is high. The reaction kinetics with activation energy of 9.783 kJ/mol was analyzed by shrinking core model, and the whole transformation process is controlled by solid product layer diffusion. A semi-empirical kinetics equation was obtained to describe the conversion process.
