为研究具有良好活性的低温选择性催化还原催化剂,针对目前Mn基材料低温选择性催化还原脱硝催化剂研究的局限性,以超氧自由基促进光催化为理论基础,N掺杂改性非金属为研究思路,采用溶胶凝胶法及过量浸渍法制备了N掺杂MnOx/TiO2催化剂,用...为研究具有良好活性的低温选择性催化还原催化剂,针对目前Mn基材料低温选择性催化还原脱硝催化剂研究的局限性,以超氧自由基促进光催化为理论基础,N掺杂改性非金属为研究思路,采用溶胶凝胶法及过量浸渍法制备了N掺杂MnOx/TiO2催化剂,用于锅炉烟气脱硝。提出了氧浓度、[NH3]/[NO]以及空速对脱硝效率的影响,结合X射线衍射表征,获得了N掺杂催化剂的反应工艺参数和相应的晶型变化特性。研究结果表明,N掺杂后,催化剂脱硝活性明显,并对催化剂N掺杂量、Mn负载量及催化剂煅烧温度进行了优化,并对优化结果进行分析。在此基础上,考察了含氧量,得出在O2浓度5%、[NH3]/[NO]为1.2时,空速28 000 h 1,反应温度180℃的条件下,掺N量为1%以及Mn负载量为5%的N掺杂MnOx/TiO2催化剂的脱硝活性稳定在90%左右。展开更多
Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by...Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by the lack of highly reactive and selective electrocatalysts .Herein, for the first time, nickel foam supported Co_(4) N was designed as a high-performance NITRR catalyst by an in-situ nonmetal leaching-induced strategy.At the optimal potential, the Co_(4) N/NF catalyst achieves ultra-high Faraday efficiency and NH_(3) selectivity of 95.4% and 99.4%, respectively.Ex situ X-ray absorption spectroscopy (XAS), together with other experiments powerfully reveal that the nitrogen vacancies produced by nitrogen leaching are stable and play a key role in boosting nitrate reduction to ammonia.Theoretical calculations confirm that Co_(4) N with abundant nitrogen vacancies can optimize the adsorption energies of NO_(3)^(-) and intermediates, lower the free energy (Δ G ) of the potential-determining step (*NH_(3) to NH_(3) ) and inhibit the formation of N-containing byproducts.In addition, we also conclude that the nitrogen vacancies can stabilize the adsorbed hydrogen, making H_(2) quite difficult to produce, and lowering ΔG from *NO to *NOH, which facilitates the selective reduction of nitrate.This study reveals significant insights about the in-situ nonmetal leaching to enhance the NITRR activity.展开更多
文摘为研究具有良好活性的低温选择性催化还原催化剂,针对目前Mn基材料低温选择性催化还原脱硝催化剂研究的局限性,以超氧自由基促进光催化为理论基础,N掺杂改性非金属为研究思路,采用溶胶凝胶法及过量浸渍法制备了N掺杂MnOx/TiO2催化剂,用于锅炉烟气脱硝。提出了氧浓度、[NH3]/[NO]以及空速对脱硝效率的影响,结合X射线衍射表征,获得了N掺杂催化剂的反应工艺参数和相应的晶型变化特性。研究结果表明,N掺杂后,催化剂脱硝活性明显,并对催化剂N掺杂量、Mn负载量及催化剂煅烧温度进行了优化,并对优化结果进行分析。在此基础上,考察了含氧量,得出在O2浓度5%、[NH3]/[NO]为1.2时,空速28 000 h 1,反应温度180℃的条件下,掺N量为1%以及Mn负载量为5%的N掺杂MnOx/TiO2催化剂的脱硝活性稳定在90%左右。
基金financial supports from National Natural Science Foundation of China(Nos.91741105,22006120)Program for Innovation Team Building at Institutions of Higher Education in Chongqing(No.CXTDX201601011)Chongqing Municipal Natural Science Foundation(No.cstc2018jcyjAX0625).
文摘Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by the lack of highly reactive and selective electrocatalysts .Herein, for the first time, nickel foam supported Co_(4) N was designed as a high-performance NITRR catalyst by an in-situ nonmetal leaching-induced strategy.At the optimal potential, the Co_(4) N/NF catalyst achieves ultra-high Faraday efficiency and NH_(3) selectivity of 95.4% and 99.4%, respectively.Ex situ X-ray absorption spectroscopy (XAS), together with other experiments powerfully reveal that the nitrogen vacancies produced by nitrogen leaching are stable and play a key role in boosting nitrate reduction to ammonia.Theoretical calculations confirm that Co_(4) N with abundant nitrogen vacancies can optimize the adsorption energies of NO_(3)^(-) and intermediates, lower the free energy (Δ G ) of the potential-determining step (*NH_(3) to NH_(3) ) and inhibit the formation of N-containing byproducts.In addition, we also conclude that the nitrogen vacancies can stabilize the adsorbed hydrogen, making H_(2) quite difficult to produce, and lowering ΔG from *NO to *NOH, which facilitates the selective reduction of nitrate.This study reveals significant insights about the in-situ nonmetal leaching to enhance the NITRR activity.
