Engineering of oxygen vacancy and bismuth cluster assisted ultrathin Bi_(12)O_(17)Cl_(2)nanosheets with efficient and selective photoreduction of CO_(2)to CO

The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to CO using ultrathin Bi_(12)O_(17)Cl_(2)nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies(OVs).The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO_(2)–CO conversion(64.3μmol g^(−1)h^(−1))and perfect selectivity.The OVs on the facet(001)of the ultrathin Bi_(12)O_(17)Cl_(2)nanosheets serve as sites for CO_(2)adsorption and activation sites,capturing photoexcited electrons and prolonging light absorption due to defect states.In addition,the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect.This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts,capable of being used for the elimination and conversion of CO_(2)in terms of energy and environment.

Exploring the impact of economic growth and energy consumption on SO_(2) emissions in China based on the Environmental Kuznets Curve hypothesis

This study aims to analysis the influence of economic growth(EG)and energy consumption(EC)on sulfur dioxide emissions(SE)in China.Accordingly,this study explores the link between EG,EC,and SE for 30 provinces in China over the span of 2000-2019.This study also analyzes cross-sectional dependence tests,panel unit root tests,Westerlund panel cointegration tests,Dumitrescu-Hurlin(D-H)causality tests.According to the test results,there is an inverted U-shaped association between EG and SE,and the assumption of the Environmental Kuznets Curve(EKC)is verified.The signs of EG and EC in the fixed effect(FE)and random effect(RE)methods are in line with those in the dynamic ordinary least squares(DOLS),fully modified ordinary least squares(FMOLS)and autoregressive distributed lag(ARDL)estimators.Moreover,the results verified that EC can obviously positive impact the SE.To reduce SE in China,government and policymakers can improve air quality by developing cleaner energy sources and improving energy efficiency.This requires the comprehensive use of policies,regulations,economic incentives,and public participation to promote sustainable development.

SO_(2)和NO_(2)在白云母表面的非均相反应研究

白云母是大气中矿物气溶胶的重要组分之一,研究大气中常见气体在其表面的非均相反应,在一定程度上可揭示大气环境中化学反应过程。文章采用自制石英玻璃微型反应器研究了SO_(2)和NO_(2)在白云母颗粒物表面的非均相反应,并探讨了相对湿度(RH)及光照对该反应的影响。结果表明,白云母对SO_(2)和NO_(2)均有一定的吸附活性,有紫外光和无紫外光条件下,SO_(2)的反应产物分别以SO_(4)^(2-)和SO_(3)^(2-)为主,NO_(2)的产物均以NO_(3)^(-)为主;RH或者紫外光照对反应均具有促进作用,两者对硫酸盐和硝酸盐的生成有协同效应;当SO_(2)和NO_(2)在白云母表面共存时,既有协同作用又存在竞争反应,SO_(4)^(2-)和NO_(3)^(-)的生成量分别是SO_(2)、NO_(2)单独存在的2.09倍和77%。因此,NO_(2)能促进硫酸盐的生成,但SO_(2)对硝酸盐的生成有明显抑制作用。

介质阻挡放电脱除NO_(x)、SO_(2)和Hg^(0)研究进展

燃煤污染物的排放为环境带来负担,减少燃煤烟气污染是控制大气环境污染的重要措施,脱硫脱硝脱汞则是烟气污染控制的重点。综述现有介质阻挡放电脱除燃煤烟气污染物研究,介绍介质阻挡放电脱除燃煤污染物机理,分析了不同结构介质阻挡放电反应器的放电原理及应用场景,主要包括空间型介质阻挡放电、沿面型介质阻挡放电、共面型介质阻挡放电、填充型介质阻挡放电和两段式介质阻挡放电;归纳了反应器反应参数、气体成分以及气体间的相互作用对脱除NO_(x)、SO_(2)和Hg^(0)的影响。讨论了催化剂协同介质阻挡放电脱除燃煤污染物与单介质阻挡放电脱除污染物的区别。确定高效率脱除NO_(x)、SO_(2)和Hg^(0)的最佳方式。随介质阻挡放电的电压和频率增加,污染物脱除效率呈增加趋势,但频率进一步增加会降低脱除效率。O_(2)在一定范围内可促进NO和Hg的氧化。微量H_(2)O在高能电子作用下产生OH^(-)和HO_(2-),从而促进SO_(2)和Hg氧化;但过量H_(2)O会抑制污染物脱除。NH3能促进NO和SO_(2)的氧化。介质阻挡放电通过激活催化剂表面产生电子和空穴,促进NO、SO_(2)和Hg^(0)的氧化,从而具有更优的污染物氧化性能。

赤泥掺杂提高CaO对SO_(2)和NO吸附性能的机理

赤泥中富含的氧化铁具有催化作用,掺杂一定比例赤泥可用于改性Ca基脱硫脱硝吸附剂。为探究赤泥掺杂对钙基吸附剂脱硫和脱硝性能提升的影响机理,采用挤压成型法制备了不同掺杂比例的赤泥/CaO吸附剂,利用固定床反应器系统,模拟实际烟气环境,开展了吸附性能试验研究和DFT模拟研究。基于密度泛函理论,构建了CaO(001)表面模型和Fe-CaO(001)表面模型,并通过对微观原子层面的计算和分析,揭示了赤泥掺杂对CaO吸附SO_(2)和NO性能的影响。试验结果表明,当赤泥添加量为5%时,赤泥/CaO吸附剂显著延长了对SO_(2)的高效吸附时间,并显著提升了对NO的吸附效率,由62.5%提高至84.0%,证实了赤泥掺杂对提高吸附剂性能的有效性。模拟计算结果表明,赤泥掺杂将SO_(2)和NO的吸附能分别由-1.181、-0.601 eV降至-2.247、-0.977 eV。此外,掺杂赤泥后,Fe原子、O原子和S原子(或N原子)之间的相互作用产生了高态密度的3个原子电子轨道共振峰,这表明赤泥掺杂增强了CaO结构的稳定性,并加强了Fe原子与O原子之间的相互作用,从而提高了O原子的活性。因此,赤泥掺杂提高了CaO对于SO_(2)和NO的化学吸附性能。

盐碱土壤水溶性Cl^(-)、NO_(3)^(-)、SO_(4)^(2-)离子提取与离子色谱仪同时测定技术研究

为建立盐碱土中水溶性Cl^(-)、NO_(3)^(-)和SO_(4)^(2-)的提取与离子色谱仪同时测定的方法,选取采自新疆和宁夏2个盐碱地土样进行正交试验,优化土壤水溶性阴离子浸提过程,水土比例对水溶性离子的测定结果影响显著。选择浸提条件为水土比例5∶1,振荡时间为3 min,浸提液离心后过0.45μm滤膜,待测液Cl^(-)、NO_(3)^(-)、SO_(4)^(2-)采用离子色谱同时测定。结果表明,离子色谱法测定3种离子线性范围均为0.2~20 mg/L;方法检出限Cl^(-)为0.18 mg/kg,NO_(3)^(-)为0.12 mg/kg,SO_(4)^(2-)为0.38 mg/kg。3种离子6次测定结果相对标准偏差均<5%;加标回收率90.6%~104%;11种不同地点的盐碱土土壤水溶性盐浸提液中Cl^(-)、NO_(3)^(-)、SO_(4)^(2-)的测定结果分别与电位滴定法、连续流动分析仪法、硫酸钡质量法测定数值之间具有较好的相关性。本方法的检出限、准确度、精密度能满足盐碱土土壤水溶性Cl^(-)、NO_(3)^(-)和SO_(4)^(2-)离子含量的同时测定,省时省力。

Cu-Based Materials for Enhanced C_(2+) Product Selectivity in Photo-/Electro-Catalytic CO_(2) Reduction: Challenges and Prospects

Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.

循环流化床NOx和SO_(2)协同脱除技术试验研究

结合循环流化床后燃技术(简称“后燃技术”)和炉内喷钙脱硫技术,在0.1 MW循环流化床试验台上研究了循环流化床NOx和SO_(2)协同脱除潜力,主要研究了后燃室脱硫剂添加量对NOx和SO_(2)排放影响以及炉内添加脱硫剂时燃烧温度对NOx和SO_(2)排放的影响。结果表明:通过后燃室注入脱硫剂可以降低SO_(2)排放,能够达到一定的脱硫效果。当燃烧温度较高时,后燃技术下炉内添加脱硫剂,脱硫效果很差。通过适当降低燃烧温度可以实现NOx和SO_(2)的协同脱除。当温度为845℃时,后燃技术下炉内脱硫时可直接实现超低NOx排放,而SO_(2)排放可以降至92.09 mg/m^(3)。后燃技术下炉内低温脱硫时,如果后燃室添加适量脱硫剂,则SO_(2)排放可进一步降低,有望实现NOx和SO_(2)双超低排放,进一步降低循环流化床污染物脱除成本。

The photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)for stable photocatalytic CO_(2)reduction

Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.

Understanding Bridging Sites and Accelerating Quantum Efficiency for Photocatalytic CO_(2) Reduction

We report a novel double-shelled nanoboxes photocatalyst architecture with tailored interfaces that accelerate quantum efficiency for photocatalytic CO_(2) reduction reaction(CO_(2)RR)via Mo–S bridging bonds sites in S_(v)–In_(2)S_(3)@2H–MoTe_(2).The X-ray absorption near-edge structure shows that the formation of S_(v)–In_(2)S_(3)@2H–MoTe_(2) adjusts the coordination environment via interface engineering and forms Mo–S polarized sites at the interface.The interfacial dynamics and catalytic behavior are clearly revealed by ultrafast femtosecond transient absorption,time-resolved,and in situ diffuse reflectance–Infrared Fourier transform spectroscopy.A tunable electronic structure through steric interaction of Mo–S bridging bonds induces a 1.7-fold enhancement in S_(v)–In_(2)S_(3)@2H–MoTe_(2)(5)photogenerated carrier concentration relative to pristine S_(v)–In_(2)S_(3).Benefiting from lower carrier transport activation energy,an internal quantum efficiency of 94.01%at 380 nm was used for photocatalytic CO_(2)RR.This study proposes a new strategy to design photocatalyst through bridging sites to adjust the selectivity of photocatalytic CO_(2)RR.

Surface engineering of ZnO electrocatalyst by N doping towards electrochemical CO_(2) reduction

The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.

The KEu(WO_(4))_(2)Red Phosphor Co-doped with Li^(+)and SO_(4)^(2-)for Synergistic Enhancement of High Efficiency and Thermal Stability

A series of tungstate red phosphors K_(1-x)Li_(x)Eu(WO_(4))_(2-y)(SO_(4))_(y)were successfully prepared by sol-gel method,and the effects of the introduction of Li~+and SO_(4)^(2-)on the fluorescence intensity and thermal quenching properties of the prepared K_(1-x)Li_(x)Eu(WO_(4))_(2-y)(SO_(4))_(y)phosphors were investigated.The X-ray diffraction data show that the prepared(Li^(+)and SO_(4)^(2-))-doped KEu(WO_(4))_(2)phosphors have a monoclinic tetragonal structure.In addition,the emission intensities of all the observed emission peaks change significantly with the increase of Li~+doping concentration,especially the intensity of the emission peaks at 615 nm fluctuated significantly and reached the maximum at x=0.3 and y=0.2.The K_(1-x)Li_(x)Eu(WO_(4))_(2-y)(SO_(4))_(y)phosphors are found to have the highest fluorescence intensity at x=0.3 and y=0.2.Moreover,the K_(0.7)Li_(0.3)Eu(WO_(4))_(1.8)(SO_(4))_(0.2)phosphor has better thermal quenching properties and luminescence efficiency,and the experimental results indicates that the fluorescence intensity and thermal burst performance of KEu(WO_(4))_(2)red phosphor could be effectively improved by using low-cost bionic doping of Li^(+)and SO_(4)^(2-).

Highly defective HKUST-1 with excellent stability and SO_(2) uptake: The hydrophobic armor effect of functionalized ionic liquids

Water stability is one of the most important factors restricting the practical application of metal organic frameworks (MOFs). In this work, wefabricate a highly defective HKUST-1 framework with a mixed valence of CuI/CuIIby mechanical ball milling method. This defective HKUST-1is embellished by functionalized ionic liquids as hydrophobic armor, making the hybrid HIL1@HKUST-1 exhibits outstanding water stability,remarkable SO_(2) adsorption (up to 5.71 mmol g^(-1)), and record-breaking selectivity (1070 for SO_(2)/CO_(2) and 31,515 for SO_(2)/N_(2)) at 25 ℃ and0.1 bar, even in wet conditions.

A cascade of in situ conversion of bicarbonate to CO_(2) and CO_(2) electroreduction in a flow cell with a Ni-N-S catalyst

Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electrochemical reduction of HCO_(3)^(-)is challenging due to the inaccessible of negatively charged molecular groups to the electrode surface.Herein,we adopt a comprehensive strategy to tackle this challenge,i.e.,cascade of in situ chemical conversion of HCO_(3)^(-)to CO_(2) and CO_(2) electrochemical reduction in a flow cell.With a tailored Ni-N-S single atom catalyst(SACs),where sulfur(S)atoms located in the second shell of Ni center,the CO_(2)electroreduction(CO_(2)ER)to CO is boosted.The experimental results and density functional theory(DFT)calculations reveal that the introduction of S increases the p electron density of N atoms near Ni atom,thereby stabilizing^(*)H over N and boosting the first proton coupled electron transfer process of CO_(2)ER,i.e.,^(*)+e^(-)+^(*)H+^(*)CO_(2)→^(*)COOH.As a result,the obtained catalyst exhibits a high faradaic efficiency(FE_(CO)~98%)and a low overpotential of 425 mV for CO production as well as a superior turnover frequency(TOF)of 47397 h^(-1),outcompeting most of the reported Ni SACs.More importantly,an extremely high FECOof 90%is achieved at 50 mA cm^(-2)in the designed membrane electrode assembly(MEA)cascade electrolyzer fed with liquid bicarbonate.This work not only highlights the significant role of the second coordination on the first coordination shell of the central metal for CO_(2)ER,but also provides an alternative and feasible strategy to realize the electrochemical conversion of HCO_(3)^(-)to high-value chemicals.

“Blocking and rebalance”mechanism-guided design strategies of bimetallic doped 2D a-phosphorus carbide as efficient catalysts for N_(2) electroreduction

Compared to single atom catalysts(SACs),the introduction of dual atom catalysts(DACs)has a significantly positive effect on improving the efficiency in the electrocatalytic nitrogen reduction reaction(NRR)which provides an environmental alternative to the Haber-Bosch process.However,the research on the mechanism and strategy of designing bimetallic combinations for better performance is still in its early stages.Herein,based on"blocking and rebalance"mechanism,45 combinations of bimetallic pair dopedα-phosphorus carbide(TM_(A)TM_(B)@PC)are investigated as efficient NRR catalysts through density functional theory and machine learning method.After a multi-step screening,the combinations of TiV,TiFe,MnMo,and FeW exhibit highly efficient catalytic performance with significantly lower limiting potentials(-0.17,-0.18,-0.14,and-0.30 V,respectively).Excitingly,the limiting potential for CrMo and CrW combinations is 0 V,which are considered to be extremely suitable for the NRR process.The mechanism of"blocking and rebalance"is revealed by the exploration of charge transfer for phosphorus atoms in electron blocking areas.Moreover,the descriptorφis proposed with machine learning,which provides design strategies and accurate prediction for finding efficient DACs.This work not only offers promising catalysts TM_(A)TM_(B)@PC for NRR process but also provides design strategies by presenting the descriptorφ.

Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO_(2)reduction and aryl alcohol oxidation

Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.

Nickel-Nitrogen-Carbon(Ni-N-C)Electrocatalysts Toward CO_(2)electroreduction to CO:Advances,Optimizations,Challenges,and Prosoects

Electrocatalytic reduction of CO_(2)into high energy-density fuels and value-added chemicals under mild conditions can promote the sustainable cycle of carbon and decrease current energy and environmental problems.Constructing electrocatalyst with high activity,selectivity,stability,and low cost is really matter to realize industrial application of electrocatalytic CO_(2)reduction(ECR).Metal-nitrogen-carbon(M-N-C),especially Ni-N-C,display excellent performance,such as nearly 100%CO selectivity,high current density,outstanding tolerance,etc.,which is considered to possess broad application prospects.Based on the current research status,starting from the mechanism of ECR and the existence form of Ni active species,the latest research progress of Ni-N-C electrocatalysts in CO_(2)electroreduction is systematically summarized.An overview is emphatically interpreted on the regulatory strategies for activity optimization over Ni-N-C,including N coordination modulation,vacancy defects construction,morphology design,surface modification,heteroatom activation,and bimetallic cooperation.Finally,some urgent problems and future prospects on designing Ni-N-C catalysts for ECR are discussed.This review aims to provide the guidance for the design and development of Ni-N-C catalysts with practical application.

Cobalt phthalocyanine promoted copper catalysts toward enhanced electro reduction of CO_(2)to C_(2):Synergistic catalysis or tandem catalysis?

The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.

A dendritic Cu/Cu_(2)O structure with high curvature enables rapid and efficient reduction of carbon dioxide to C_(2) in an H-cell

Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multicarbon products is an efficient approach for ad-dressing the energy crisis and achieving carbon neutrality.In H-cells,achieving high-current C_(2)products is challenging because of the inefficient mass transfer of the catalyst and the presence of the hydrogen evolution reaction(HER).In this study,dendritic Cu/Cu_(2)O with abundant Cu^(0)/Cu^(+)interfaces and numerous dendritic curves was synthesized in a CO_(2)atmosphere,resulting in the high selectivity and current density of the C_(2)products.Dendritic Cu/Cu_(2)O achieved a C_(2)Faradaic efficiency of 69.8%and a C_(2)partial current density of 129.5 mA cm^(-2)in an H-cell.Finite element simulations showed that a dendritic structure with a high curvature generates a strong electric field,leading to a localized CO_(2)concentration.Additionally,DRT analysis showed that a dendritic struc-ture with a high curvature actively adsorbed the surrounding high concentration of CO_(2),enhancing the mass transfer rate and achieving a high current density.During the experiment,the impact of the electronic structure on the performance of the catalyst was investigated by varying the atomic ratio of Cu^(0)/Cu^(+) on the catalyst surface,which resulted in improved ethylene selectivity.Under the optimal atomic ratio of Cu^(0)/Cu^(+),the charge transfer resistance was minimized,and the desorption rate of the intermediates was low,favoring C_(2) generation.Density functional theory calculations indicated that the Cu^(0)/Cu^(+) interfaces exhibited a lower Gibbs free energy for the rate-determining step,enhancing C_(2)H_(4) formation.The Cu/Cu_(2)O catalyst also exhibited a low Cu d-band center,which enhanced the adsorption stability of *CO on the surface and facilitated C_(2)formation.This observa-tion explained the higher yield of C_(2) products at the Cu^(0)/Cu^(+) interface than that of H_(2) under rapid mass transfer.The results of the net present value model showed that the H-cell holds promising industrial prospects,contingent upon it being a catalyst with both high selectivity and high current density.This approach of integrating the structure and composition provides new insights for ad-vancing the CO_(2)RR towards high-current C_(2) products.

Ligand modulation of active center to promote lead-free Cs_(2)AgInCl_(6)photocatalytic CO_(2)reduction

Metal halide perovskites(MHP)are potential candidates for the photocatalytic reduction of CO_(2)due to their long photogenerated carrier lifetime and charge diffusion length.However,the conventional long-chain ligand impedes the adsorption and activation of CO_(2)molecules in practical applications.Here,a ligand modulation technology is employed to enhance the photocatalytic CO_(2)reduction activity of lead-free Cs_(2)AgInCl_(6)microcrystals(MCs).The Cs_(2)AgInCl_(6)MCs passivated by Oleic acid(OLA)and Octanoic acid(OCA)are used for photocatalytic CO_(2)reduction.The results show that the surface defects and electronic properties of Cs_(2)AgInCl_(6)MCs can be adjusted through ligand modulation.Compared with the OLA-Cs_(2)AgInCl_(6),the OCA-Cs_(2)AgInCl_(6)catalyst demonstrated a significant improvement in the catalytic yield of CO and CH_(4).The CO and CH_(4)catalytic yields of OCA-Cs_(2)AgInCl_(6)reached 171.88 and34.15μmol g^(-1)h^(-1)which were 2.03 and 12.98 times higher than those of OLA-Cs_(2)AgInCl_(6),and the total electron consumption rate of OCA-Cs_(2)AgInCl_(6)was 615.2μmol g^(-1)h^(-1)which was 3.25 times higher than that of OLA-Cs_(2)AgInCl_(6).Furthermore,in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs_(2)AgInCl_(6)MCs induced by ligand modulation.This study illustrates the potential of lead-free Cs_(2)AgInCl_(6)MCs for efficient photocatalytic CO_(2)reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.