蝶翅构型TiO2/等离子体纳米金复合体系全光谱二氧化碳光还原特性研究

以红珠灰蝶为生物模板,使用原子层沉积法构筑三维构型TiO_2光催化材料以增强其光捕获能力;使用种子生长法制备具有宽幅可见光波段吸收能力的等离子体共振金纳米棱结构,并将其负载于蝶翅构型TiO_2上以得到全光谱响应的复合光催化体系;采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见分光光度计、X射线衍射仪(XRD)等表征了所制备的样品;对样品进行了二氧化碳还原性能测试,结果表明在全光谱照射下,负载有金纳米棱的蝶翅构型TiO_2的二氧化碳光还原性能比无结构的提升了54%。

石墨相氮化碳的异质结结构在光催化领域的研究进展

近年来,石墨相氮化碳(g-C_(3)N_(4))因具有适宜的导带价带位置及低成本、低毒性、可见光驱动、稳定性好等特点在光驱动环境催化和新能源催化等领域受到广泛关注.然而,其光生电子空穴对复合严重的问题,影响了石墨相氮化碳在各种光催化反应中的催化活性.由于石墨相氮化碳的异质结结构能够有效抑制光生电子空穴对的复合并改善光生载流子的利用效率,因而其成为了光催化领域的研究热点.综述了过去5年中石墨相氮化碳的异质结结构在污染物光催化降解、光催化水分解产氢、二氧化碳光催化还原领域的研究进展,以期为石墨相氮化碳基材料在光催化领域的发展提供理论支持.

Boosting CO_(2) photoreduction by synergistic optimization of multiple processes through metal vacancy engineering

The photoreduction of greenhouse gas CO_(2) using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of CO_(2) photoreduction remains generally low due to the challenging activation of CO_(2) and the limited light absorption and separation of charge.Defect engineering of catalysts rep-resents a pivotal strategy to enhance the photocatalytic activity for CO_(2),with most research on met-al oxide catalysts focusing on the creation of anionic vacancies.The exploration of metal vacancies and their effects,however,is still underexplored.In this study,we prepared an In2O3 catalyst with indium vacancies(VIn)through defect engineering for CO_(2) photoreduction.Experimental and theo-retical calculations results demonstrate that VIn not only facilitate light absorption and charge sepa-ration in the catalyst but also enhance CO_(2) adsorption and reduce the energy barrier for the for-mation of the key intermediate*COOH during CO_(2) reduction.Through metal vacancy engineering,the activity of the catalyst was 7.4 times,reaching an outstanding rate of 841.32μmol g(-1)h^(-1).This work unveils the mechanism of metal vacancies in CO_(2) photoreduction and provides theoretical guidance for the development of novel CO_(2) photoreduction catalysts.

单原子催化:追寻催化领域的“圣杯”

在催化领域,“圣杯”反应是指对人类未来具有显著的科学、经济和环境可持续性价值的反应.这些反应利用地球上丰富易得的资源,如CH_(4),H_(2)O,CO_(2)和N_(2)等,生产各种有价值的化工产品.尽管意义重大,但由于反应物的化学惰性和产物相对活泼的特点,反应的转化率通常较低,对目标产物的选择性较差.目前,降低“圣杯”反应的活化能垒仍然是一个巨大的挑战,需要开发新型催化剂来应对以上挑战.单原子催化剂(SAC)含有部分带电的金属单原子物种,具有明确的、可调的结构,是一类很有前途的负载型催化剂,不仅可以提升催化性能,也为深入了解反应机制和构效关系提供便利.本文总结和评价了SAC在五个“圣杯”反应中的最新应用.围绕甲烷活化,介绍了甲烷温和氧化制甲醇和无氧甲烷偶联两类反应.热催化甲烷氧化通常需要引入共还原剂来提升催化活性,因此所采用的SAC通过多位点协同作用,实现串联催化过程以有效活化甲烷;而光催化过程则可在无共还原剂的情况下,通过不同单原子金属位点(如Au,Pd,Fe,W)与水或O_(2)的作用,产生活性氧物种,实现甲烷活化.目前用于甲烷氧化的SAC仍缺乏统一的设计和优化标准,在效率提升和机理研究等方面有很大发展空间.对于无氧甲烷偶联反应,目前开发的SAC主要有Fe,Pt和Pd基催化剂,其中单原子位点有助于抑制积碳,提升性能稳定性和产物选择性.然而,部分SAC在高温无氧气氛下难以维持其单原子结构,仍需进一步探索和优化.随后介绍了两种人工光合成反应,即水分解产氢和CO_(2)还原.对于光催化产氢,SAC独特且结构明确的位点可显著提升产氢乃至全解水的性能,也可用于产氢机理的深入研究.对于光催化CO_(2)还原,重点介绍了对生成CO,CH_(4)和CH_3OH具有高选择性的SAC,其中,单原子位点对于调节小分子中间体的吸附起到了重要作用,从而影响了选择性.许多用于人工光合成的SAC存在不止一种催化位点,这些位点可以协同提升目标反应的效率.最后,展示了SAC用于氮气活化合成氨的研究进展,大多采用非贵金属位点(如Fe,Co和La),通过特定的配位结构实现与N_(2)的特殊作用,以有效削弱N≡N键强度.本文最后总结了SAC在“圣杯”反应中的优势和面临的诸多挑战,并提出了该领域未来可能的发展方向,其中包括深入探究机理和构效关系,结合先进信息技术高效筛选符合条件的催化剂,以及设计新型催化位点以扩大催化材料的应用领域.

改性TiO_2纳米粒子用于可见光催化反应

采用原位溶胶-凝胶法合成氧化钛,同时对大环配合物进行改性,得到粒径为10.89 nm的纳米级钴酞菁改性氧化钛(CoPc/TiO2)光催化剂,用于可见光下、水溶液中CO2的还原反应,可得HCHO、CH3OH、HCOOH等产物。结果表明,由于金属酞菁的存在导致TiO2粒径减小,相转变温度降低,CoPc以单体形式均匀分散于TiO2凝胶基质中,其二聚及多聚倾向大大减弱。钴酞菁固载的催化剂给电子能力较强,极大地提高了光还原效率。光反应的最佳条件为:在0.1 mol/L的NaOH溶液中,0.15 g CoPc/TiO2催化剂,三乙胺和三乙醇胺作为电子供体催化效果较好,在可见光照反应10 h后,还原产物中总有机碳最高可达2 965.3μmol/g-cat。在还原过程中CO2主要以HCO3-的形式被还原而非碳酸根离子,而且HCO3-的浓度在0.2 mol/L时还原产物量最大。

Synthesis of bionic-macro/microporous MgO-modified TiO_2 for enhanced CO_2 photoreduction into hydrocarbon fuels

The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2 . The photocatalytic reduction of CO2 with H2O vapor into hydrocarbon fuel was studied with these MgO-TiO2 nanostructures as the photocatalysts with the benefits of improved CO2 adsorption and activation through incorporated MgO. Various factors involving CO2 adsorption capacity, migration of charge carriers to the surface, and the number of activity sites, which depend on the amount of added MgO, determine the photocatalytic conversion efficiency.

Octahedral Cu_2O-modified TiO_2 nanotube arrays for efficient photocatalytic reduction of CO_2

A photocatalyst composed of TiO 2 nanotube arrays（TNTs） and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time（5 min） resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time（45 min） gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.

Co-MOF as an electron donor for promoting visible-light photoactivities of g-C3N4 nanosheets for CO2 reduction

A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride(g-C3N4)nanosheets for CO2 reduction via coupling with the electron donor Co-metal-organic framework(MOF)is proposed in this study.Specifically,Co-MOF as an electron donor is capable of transferring the photogenerated electrons in the lowest unoccupied molecular orbital(LUMO)to the conduction band of g-C3N4 to facilitate charge separation.As expected,the prepared Co-MOF/g-C3N4 nanocomposites display excellent visible-light-driven photocatalytic CO2 reduction activities.The CO production rate of 6.75μmol g–1 h–1 and CH4 evolution rate of 5.47μmol g–1 h–1 are obtained,which are approximately 2 times those obtained with the original g-C3N4 under the same conditions.Based on a series of analyses,it is shown that the introduction of Co-MOF not only broadens the range of visible-light absorption but also enhances the charge separation,which improves the photocatalytic activity of g-C3N4 to a higher level.In particular,the hydroxyl radical(·OH)experiment was operated under 590 nm(single-wavelength)irradiation,which further proved that the photogenerated electrons in the LUMO of Co-MOF can successfully migrate to g-C3N4.This work may provide an important strategy for the design of highly efficient g-C3N4-based photocatalysts for CO2 reduction.

A review on TiO_2-based Z-scheme photocatalysts

TiO2‐based Z‐scheme photocatalysts have attracted considerable attention because of the low recombination rate of their photogenerated electron–hole pairs and their high photocatalytic efficiency.In this review,the reaction mechanism of Z‐scheme photocatalysts,recent research progress in the application of TiO2‐based Z‐scheme photocatalysts,and improved methods for photocatalytic performance enhancement are explored.Their applications,including water splitting,CO2reduction,decomposition of volatile organic compounds,and degradation of organic pollutants,are also described.The main factors affecting the photocatalytic performance of TiO2‐based Z‐scheme photocatalysts,such as pH,conductive medium,cocatalyst,architecture,and mass ratio,are discussed.Concluding remarks are presented,and some suggestions for the future development of TiO2‐based Z‐scheme photocatalysts are highlighted.

Interfacial engineering of graphitic carbon nitride(g-C_3N_4)-based metal sulfide heterojunction photocatalysts for energy conversion: A review

As one of the most appealing and attractive technologies, photocatalysis is widely used as a promising method to circumvent the environmental and energy problems. Due to its chemical stability and unique physicochemical, graphitic carbon nitride (g-C3N4) has become research hotspots in the community. However, g-C3N4 photocatalyst still suffers from many problems, resulting in unsatisfactory photocatalytic activity such as low specific surface area, high charge recombination and insufficient visible light utilization. Since 2009, g-C3N4-based heterostructures have attracted the attention of scientists worldwide for their greatly enhanced photocatalytic performance. Overall, this review summarizes the recent advances of g-C3N4-based nanocomposites modified with transition metal sulfide (TMS), including (1) preparation of pristine g-C3N4,(2) modification strategies of g-C3N4,(3) design principles of TMS-modified g-C3N4 heterostructured photocatalysts, and (4) applications in energy conversion. What is more, the characteristics and transfer mechanisms of each classification of the metal sulfide heterojunction system will be critically reviewed, spanning from the following categories:(1) Type I heterojunction,(2) Type II heterojunction,(3) p-n heterojunction,(4) Schottky junction and (5) Z-scheme heterojunction. Apart from that, the application of g-C3N4-based heterostructured photocatalysts in H2 evolution, CO2 reduction, N2 fixation and pollutant degradation will also be systematically presented. Last but not least, this review will conclude with invigorating perspectives, limitations and prospects for further advancing g-C3N4-based heterostructured photocatalysts toward practical benefits for a sustainable future.

Supercritical synthesis of platinum-modified titanium dioxide for solar fuel production from carbon dioxide

This paper investigates the properties of TiO2‐based photocatalysts synthesised under supercriticalconditions.Specifically,the characteristics of Pt dispersed on TiO2catalysts obtained in supercriticalCO2are discussed and compared with those of commercial TiO2.The photocatalytic activity of thesynthesised catalysts in the CO2photoreduction reaction to produce solar fuel is tested.The mainconclusion of the study is that photocatalysts with better or similar features,including high surfacearea,crystallisation degree,hydroxyl surface concentration,pore volume,absorbance in the visiblerange and methane production rate,to those of commercial TiO2may be produced for the reductionof CO2to fuel by synthesis in supercritical media.

Photo-thermal CO_(2) reduction with methane on group Ⅷ metals:In situ reduced WO_(3) support for enhanced catalytic activity

Photo-thermal CO_(2) reduction with methane(CRM)is beneficial for solar energy harvesting and energy storage.The search for efficient photo-thermal catalysts is of great significance.Here,we reveal that group Ⅷ metal catalysts supported by optical material WO_(3) are more effective for photo-thermal CRM,giving catalytic activities with visible light assistance that are 1.4-2.4 times higher than that achieved under thermal conditions.The activity enhancement(1.4-2.4 times)was comparable to that achieved with plasmonic-Au-promoted catalysts(1.7 times).Characterization results indicated that WO_(3) was partially reduced to WO_(3-x) in situ under the reductive CRM reaction atmosphere,and that WO_(3-x) rather than WO_(3) enhanced the activities with visible light assistance.Our method provides a promising approach for improving the activity of catalysts under light irradiation.

Photoelectrocatalytic CO2 reduction based on metalloporphyrin-modified TiO2 photocathode

The conversion of CO2 and water to value-added chemicals under sunlight irradiation, especially by photoelectrocatalytic reduction process, is always a dream for human beings. A new artificial photosynthesis system composed of a metalloporphyrin-functionalized TiO2 photocathode and BiVO4 photoanode can efficiently transform CO2 and water to methanol, which is accompanied by oxygen release. This photoelectrocatalytic system smoothly produces methanol at a rate of 55.5 μM h^–1 cm^– 2, with 0.6 V being the membrane voltage in plants. The production of hydrogen can also be observed when the voltage is more than 0.75 V, due to photocatalysis. Our results evidently indicate that the molecules of metalloporphyrin attached onto the surface of anatase (TiO2) behave as chlorophyll, NADP, and Calvin cycle in plant cells.

Layered double hydroxide photocatalysts for solar fuel production

Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energy crisis and environmental challenges.It enables not only the realization of clean,renewable,and high-heating-value solar fuels,but also the reduction of CO_(2) emissions.Layered double hydroxides(LDHs)are a type of two-dimensional anionic clay with a brucite-like structure,and are characterized by a unique,delaminable,multidimensional,layered structure;tunable intralayer metal cations;and exchangeable interlayer guest anions.Therefore,it has been widely investigated in the fields of CO_(2) reduction,photoelectrocatalytic water oxidation,and water photolysis to produce H2.However,the low carrier mobility and poor quantum efficiency of pure LDH limit its application.An increasing number of scholars are exploring methods to obtain LDH-based photocatalysts with high energy conversion efficiency,such as assembling photoactive components into LDH laminates,designing multidimensional structures,or coupling different types of semiconductors to construct heterojunctions.This review first summarizes the main characteristics of LDH,i.e.,metal-cation tunability,intercalated guest-anion substitutability,thermal decomposability,memory effect,multidimensionality,and delaminability.Second,LDHs,LDH-based composites(metal sulfide-LDH composites,metal oxide-LDH composites,graphite phase carbon nitride-LDH composites),ternary LDH-based composites,and mixed-metal oxides for splitting water to produce H_(2) are reviewed.Third,graphite phase carbon nitride-LDH composites,MgAl-LDH composites,CuZn-LDH composites,and other semiconductor-LDH composites for CO_(2) reduction are introduced.Although the field of LDH-based photocatalysts has advanced considerably,the photocatalytic mechanism of LDHs has not been thoroughly elucidated;moreover,the photocatalytic active sites,the synergy between different components,and the interfacial reaction mechanism of LDH-based photocatalysts require further investigation.Therefore,LDH composite materials for photocatalysis could be developed through structural regulation and function-oriented design to investigate the effects of different components and interface reactions,the influence of photogenerated carriers,and the impact of material composition on the physical and chemical properties of the LDH-based photocatalyst.

Harnessing the Beneficial Attributes of Ceria and Titania in a Mixed-Oxide Support for Nickel-Catalyzed Photothermal CO_2 Methanation

Solar-powered carbon dioxide （CO_2）-to-fuel conversion presents itself as an ideal solution for both CO_2 mit- igation and the rapidly growing world energy demand. In this work, the heating effect of light irradiation onto a bed of supported nickel （Ni） catalyst was utilized to facilitate CO_2 conversion. Ceria （CeO_2）-titania （TiO_2） oxide supports of different compositions were employed and their effects on photothermal CO_2 conver- sion examined, Two factors are shown to be crucial for instigating photothermal CO_2 methanation activity： ① Fine nickel deposits are required for both higher active catalyst area and greater light absorption capacity for the initial heating of the catalyst bed; and ② the presence of defect sites on the support are necessary to promote adsorption of C02 for its subsequent activation, Titania inclusion within the support plays a crucial role in maintaining the oxygen vacancy defect sites on the （titanium-doped） cerium oxide. The combination of elevated light absorption and stabilized reduced states for CO_2 adsorption subsequently invokes effective Dhotothermal CO_2 methanation when the ceria and titania are blended in the ideal ratio（s）.

Enhancing the photocatalytic activity and photostability of zinc oxide nanorod arrays via graphitic carbon mediation

Low optical absorption and photocorrosion are two crucial issues limiting the practical applications of zinc oxide(ZnO)-based photocatalysts.In this paper,we report the fabrication of graphitic-carbon-mediated ZnO nanorod arrays(NRAs)with enhanced photocatalytic activity and photostability for CO2 reduction under visible light irradiation.ZnO NRA/C-x(x=005,01,02,and 03)nanohybrids are prepared by calcining pre-synthesized ZnO NRAs with different amounts of glucose(0.05,0.1,0.2,and 0.3 g)as a carbon source via a hydrothermal method.X-ray photoelectron spectroscopy reveals that the obtained ZnO NRA/C-x nanohybrids are imparted with the effects of both carbon doping and carbon coating,as evidenced by the detected C-O-Zn bond and the C-C,C-O and C=O bonds,respectively.While the basic structure of ZnO remains unchanged,the UV-Vis absorption spectra show increased absorbance owing to the carbon doping effect in the ZnO NRA/C-x nanohybrids.The photoluminescence(PL)intensities of ZnO NRA/C-x nanohybrids are lower than that of bare ZnO NRA,indicating that the graphitic carbon layer coated on the surface of the ZnO NRA significantly enhances the charge carrier separation and transport,which in turn enhances the photoelectrochemical property and photocatalytic activity of the ZnO NRA/C-x nanohybrids for CO2 reduction.More importantly,a long-term reaction of photocatalytic CO2 reduction demonstrates that the photostability of ZnO NRA/C-x nanohybrids is significantly increased in comparison with the bare ZnO NRA.

"All‐in‐one"covalent organic framework for photocatalytic CO2 reduction

Constructed by selecting appropriate building blocks,covalent organic frameworks(COFs)can be endowed with a variety of specific functions.Herein,we successfully synthesized an imine‐linked H_(2)PReBpy‐COF with the CO_(2) reduction catalyst[ReI(bpy)(CO)_(3)Cl]and the porphyrin photosensitizer as the monomeric building units.The light‐harvesting properties of the porphyrin itself,augmented by the extendedπ‐conjugated planar structure of 2D COF,enable H_(2)PReBpy‐COF the excellent light‐harvesting capability,efficient charge separation,and fast interfacial charge transfer.In addition,a large amount of uniformly distributed[ReI(bpy)(CO)_(3)Cl]units offer H_(2)PReBpy‐COF an excellent activity toward photocatalytic CO_(2) reduction with moderate selectivity and reusability.This study demonstrated a proof of concept in which the advantages of COFs and functional monomers are rationally integrated for photocatalytic solar fuel conversion.

Hierarchical TiO2 nanorods with a highly active surface for photocatalytic CO_(2) reduction

Photocatalytic carbon dioxide reduction reaction(CO_(2)RR)has been considered as one of most effective ways to solve the current energy crisis and environmental problems.However,the practical application of photocatalytic CO_(2)RR is largely hindered by lock of efficient catalyst.Here,hierarchical titanium dioxide(TiO_(2))nanostructures with a highly active{001}surface were successfully synthesized by a facile approach from metal Ti powders.The obtained hierarchical TiO_(2)nanostructures were composed of TiO_(2)nanorods,which have a diameter about 5–10 nm and a length of several micrometers.It is found that these nanorods have exposed{001}facets.On the other hand,these hierarchical TiO_(2)nanostructures have a good light-harvesting efficiency with the help of TiO_(2)nanorods component and large specific surface area.Therefore,these hierarchical TiO_(2)nanostructures exhibit a much better activity for photocatalytic CO_(2)reduction than that of commercial TiO_(2)(P25).This high activity can be attributed to the synergistic effects of active surface,efficient charge transfer along nanorods and good light harvesting in the nanorod-hierarchical nanostructures.

MXenes as noble-metal-alternative co-catalysts in photocatalysis

Photocatalysis has become a focal point in research as a clean and sustainable technology with the potential to solve environmental problems and energy crises.The loading of noble-metal co-catalysts can substantially improve the photocatalytic efficiency of semiconductors.Because the high cost and scarcity of noble metals markedly limit their large-scale applications,finding a noble-metal-alternative co-catalyst is crucial.MXene,a novel 2D transition metal material,has attracted considerable attention as a promising substitute for noble metal co-catalysts owing to its cost-efficiency,unique 2D layered structure,and excellent electrical,optical,and thermodynamic properties.This review focuses on the latest advancements in research on MXenes as co-catalysts in relatively popular photocatalytic applications(hydrogen production,CO2 reduction,nitrogen fixation,and organic pollutant oxidation).The synthesis methods and photocatalytic mechanisms of MXenes as co-catalysts are also summarized according to the type of MXene-based material.Finally,the crucial opportunities and challenges in the prospective development of MXene-based photocatalysts are outlined.We emphasize that modern techniques should be used to demonstrate the effects of MXenes on photocatalysis and that the photocatalytic activity of MXene-based photocatalysts can be further improved using defective engineering and recent phenomena such as the localized surface plasmon resonance effect and single-atom catalysis.

Nitrate reduction by·CO_(2)^(-) from UV-activated HCOOH

To address the environmental and health hazards of nitrate(NO_(3)^(-))in water,a denitrification advanced reduction process(ARP)using only formic acid(HCOOH)activated by ultraviolet(UV)light was proposed.The efficiency,influencing factors,mechanism,and kinetics of the reduction were investigated through component analysis and radical detection.Results show that,after 90 min of UV illumination,the reduction and gas conversion ratios of 50 mg/L NO_(3)^(-)-N reach 99.9%and 99.8%,respectively,under 9 mM of C_(0)(HCOOH),pH=3.0,and N_(2) aeration.Meanwhile,96.7%of HCOOH is consumed and converted into gas.The NO_(3)^(-)-N conversion process includes the transformation to NO_(2)^(-)-N,followed by a further reduction to gas and a direct conversion into gas,introducing small amounts of nitrite and ammonia.The carbon dioxide anion radical(·CO_(2)^(-))from HCOOH/HCOO^(-)is the principal cause of NO_(3)^(-)-N reduction by UV/HCOOH/N 2 ARP.In contrast,·CO_(2)^(-)production is caused by the hydroxyl radical(·OH).The NO_(3)^(-)-N reduction efficiency is enhanced by the increase in the light intensity,considerably affected by the initial pH,and less affected by inorganic anions,including Cl^(-),H_(2)PO_(4)^(-),and HCO_(3)^(-)/CO_(3)^(2-).The initial HCOOH concentration and light intensity are the main factors that influence the NO_(3)^(-)-N reduction rate.