“环境催化城市”:概念提出和研究展望

大气污染是城市环境质量改善面临的重大挑战。城市化过程既是造成城市大气高度复合污染的重要原因,也为城市自净化大气污染物提供了可人为强化的条件。“环境催化城市”是指将城市中的建筑物内外、硬化地面等表面涂覆催化材料,在自然界的光、热等条件下实现环境中低浓度气态污染物自发催化净化的城市。构建“环境催化城市”对低碳控制大气复合污染,持续改善室内外环境空气质量,规划建设“自净城市”意义重大。本文提出了“环境催化城市”概念,并对如何完善和发展“环境催化城市”理论和实践进行了展望。

Symmetry dependent activation and reactivity of peroxysulfates on FeS_(2)(001)surface

Heterogeneous peroxysulfates-based advanced oxidation processes(AOPs)have garnered significant attention for purifying organic wastewater since they offer many advantages like low cost,safe storage,facile activation and reactive species participation[1].Nonradical and radical pathways have been proposed to be involved in peroxysulfates activation.

Boosting multi-hole water oxidation catalysis on hematite photoanodes under low bias

The accumulation of multiple surface holes is considered to be the key to efficient photoelectrochemical(PEC)water oxidation.Previous PEC water oxidation studies commonly apply high potentials(>1.2 VRHE)to achieve this key.But how to complete multi-hole transfer under low bias(<1.2 VRHE)remains unknown.Herein,we find that,on a typical visible-light photoanode,hematite(α-Fe_(2)O_(3)),UV excitation plays a indispensable role in driving multi-hole water oxidation under low bias.Compared with the visible-light excitation,the UV excitation promotes the formation of adjacent surface-trapped holes onα-Fe_(2)O_(3) at 0.9VRHE,thereby increasing the reaction order of surface holes from~1 to~2 and improving the PEC water oxidation activity by one order of magnitude.The UV irradiation reduces the formation probability of self-trapped excitons and results in~3 to 5-fold increase of surface holes.These advantages enable the UV excitation to contribute about 40%to the total photocurrent under 1 solar illumination,even though its energy only occupies 6%of the incident light.This mechanism is also applicable to boost selective two-hole oxidation of thioether at 0.1 VFc/Fc+and nitrite at 0.9 VRHE.

Solar-driven green synthesis of epoxides

Epoxides are one of the most important intermediates used in the production of valuable chemicals. Traditional preparation methods often rely on hazardous oxidants or extensive fossil fuel-powered thermal catalytic systems, resulting in significant waste production and CO_(2) emissions. Solar-driven photo(electro)chemistry is an emerging option for achieving the environmentally-friendly synthesis of epoxides. In this review, we firstly summarize the fundamental understanding of epoxidation reactions among various systems, including molecular catalysis, heterogeneous thermal catalysis and electrocatalysis. Then, we focus on the recent advances in the synthesis of epoxides achieved by photo(electro)chemical approaches. This review is concluded by the rational design of photoelectrochemical systems towards efficient epoxide synthesis.

The abatement of major pollutants in air and water by environmental catalysis

This review reports the research progress in the abatement of major pollutants in air and water by environmental catalysis. For air pollution control, the selective catalytic reduction of NOχ （SCR） by ammonia and hydrocarbons on metal oxide and zeolite catalysts are reviewed and discussed, as is the removal of Hg from flue gas by catalysis. The oxidation of Volatile organic compounds （VOCs） by photo- and thermal- catalysis for indoor air quality improvement is reviewed. For waste- water treatment, the catalytic elimination of inorganic and organic pollutants in wastewater is presented. In addition, the mechanism for the procedure of abatement of air and water pollutants by catalysis is discussed in this review. Finally, a research orientation on environment catalysis for the treatment of air pollutants and wastewater is proposed.

Identifying the active photocatalytic H2-production sites on TiO2-supported Pt nanoparticles by the in-situ infrared spectrum of CO

Identifying the active catalytic centers on catalyst surface is significant for exploring the catalytic reaction mechanism and further guiding the synthesis of high-performance catalysts.However,it remains a challange in developing the site-specific technology for the identification of the active catalytic centers.Herein,in-situ infrared spectroscopy of adsorbed CO,photocatalytic hydrogen evolution reaction(HER)test and theoretical simulation were used to distinguish and quantify the different surface sites and their H2-production catalytic activity on TiO2-supported Pt nanoparticles(Pt NPs).Two different types of surface Pt sites,tip Pt(Pttip)and edge/terrace Ptedge/terrace,on TiO2-supported Pt nanoparticles(Pt NPs)were identified.The photocatalytic H2-production activity of TiO2-supported Pt NPs shows a linear functional relationship with the number of Pttip sites.However,the number of Ptedge/terracesites produced little effect on the activity of TiO2-supported Pt NPs.First-principle simulations confirmed that H2-evolution at the Pttipsites owns a lower energy barrier than that at Ptedge/terrace.This findings would be helpful for the fabrication of high-performance Pt catalysts.

All-at-once arrangement of both oxygen atoms of dioxygen into aliphatic C(sp^(3))–C(sp^(3))bonds for hydroxyketone difunctionalization

Bothβ-andγ-hydroxyketone structures are important units in biologically active molecules,synthetic drugs and fine chemicals.Although there are some routes available for their manufacture from pre-functionalized groups on one or two matrix molecule(s),the approaches to simply and simultaneously deposit two oxygen atoms from dioxygen into two specific C(sp^(3))positions of pure saturated hydrocarbons have rarely succeeded because they are involved in the targeted activation of three inert C–Hσbonds all at once.Here,we show that a TiO_(2)-CH_(3)CN photocatalytic suspension system enables the insertion of dioxygen into one C(sp^(3))–C(sp^(3))bond of strained cycloparaffin derivatives,by which difunctionalized hydroxyketone products are obtained in a one-pot reaction.With the cleavage event to release strain as the directional driving force,as-designed photocatalytic reaction systems show 21 examples ofβ-hydroxyketone products with 31%–76%isolated yields for three-membered ring derivatives and 5 examples ofγ-hydroxyketone products with 30%–63%isolated yields for four-membered ring substrates.^(18)O isotopic labeling experiments using^(18)O2,Ti^(18)O_(2) and intentionally added H218O,respectively,indicated that both oxygen atoms of hydroxyketone products were exclusively from dioxygen,suggesting a previously unknown H^(+)/TiO_(2)-e−catalyzed arrangement pathway of the hydroperoxide intermediate to convert dioxygen into hydroxyketone units.

A review on plasmonic enhancement of activity and selectivity in electrocatalytic CO_(2)reduction

Utilizing plasmonic effects to assist electrochemical reactions exhibits a huge potential in tuning the reaction activities and product selectivity,which is most appealing especially in chemical reactions with multiple products,such as CO_(2)reduction reaction(CO_(2)RR).However,a comprehensive review of the development and the underlying mechanisms in plasmon-assisted electrocatalytic CO_(2)RR remains few and far between.Herein,the fundamentals of localized surface plasmonic resonance(LSPR)excitation and the properties of typical plasmonic metals(including Au,Ag,and Cu)are retrospected.Subsequently,the potential mechanisms of plasmonic effects(such as hot carrier effects and photothermal effects)on the reaction performance in the field of plasmon-assisted electrocatalytic CO_(2)RR are summarized,which provides directions for the future development of this field.It is concluded that plasmonic catalysts exhibit potential capabilities in enhancing CO_(2)RR while more in situ techniques are essential to further clarify the inner mechanisms.