Experimental investigation of shale breakdown pressure under liquid nitrogen pre-conditioning before nitrogen fracturing

Cryogenic fracturing with liquid nitrogen(LN_(2))offers the benefits of reducing the water consumption and adverse environmental impacts induced by water-based fracturing,as well as potentially enhancing the fracture complexity.We performed a series of laboratory experiments to explore the key mechanisms governing the breakdown pressures of shale during cryogenic fracturing.In this study,cylindrical shale samples were pre-conditioned by exposing a borehole to low-temperature LN_(2) for a certain time period,and then,the samples were fractured using gaseous N_(2) under triaxial stress and a high reservoir temperature.The effects of various key parameters on the breakdown pressure were investigated,including the duration of the low-temperature LN_(2) treatment,the confining pressure,the reservoir temperature,and the direction of the shale bedding relative to the borehole axis.The results demonstrate that the injection of low-temperature LN_(2) as a pre-fracturing fluid into a borehole can significantly reduce the breakdown pressure of the shale during subsequent nitrogen fracturing.This reduction in breakdown pressure can be further intensified by increasing the duration of the LN_(2) pre-conditioning.Without LN_(2) pre-conditioning,the breakdown pressure initially increases and then decreases with increasing reservoir temperature.When LN_(2) pre-conditioning is applied,the breakdown pressure keeps decreasing with increasing reservoir temperature.As the confining pressure increased,the breakdown pressure increased linearly in the tests with and without LN_(2) pre-conditioning.The experimental results demonstrate that LN_(2) preconditioning before N_(2) fracturing is a promising waterless fracturing technique that reduces the breakdown pressure and enhances the fracture complexity.

Effects of Reduced Nitrogen Fertilization and Biochar Application on CO_2 and N_2O Emissions from a Summer Maize-Winter Wheat Rotation Field in North China

This experiment was conducted in Xinxiang, Henan from June 2013 to June 2014. Total four treatments were designed including farmers ’ common practice （F, 250 kg/hm^2）, 80% F （LF, 200 kg/hm^2）, 80% F＋biochar （LFC） and no fertilizer （CK） to measure the dynamic emissions of CO2 and N2O from a summer maize-winter wheat field by static chamber-gas chromatography method. The results showed that the soil CO2 emission was 21.8-1 022.7 mg/（m^2·h）, and was mainly influenced by soil temperature and moisture content. During the growth of summer maize, the soil CO2 emission was more significantly affected by soil moisture con-tent; and in winter wheat growing season, it was more significantly affected by soil temperature in the top 5 cm. The LF and LFC treatments significantly reduced the soil cumulative CO2 emission, especial y during the growth of winter wheat. Fertiliza-tion and irrigation were the main factors influencing the soil N2O emission. The soil N2O emission during the fertilization period accounted for 73.9%-74.5% and 40.5%-43.6% of the soil cumulative N2O emission during the summer maize-and winter wheat-growing season, respectively. The peak of emission fluxes was determined by fertilization amount, while the occurrence time of emission peak and emission re-duction effect were influenced by irrigation. The LF treatment reduced the soil cu-mulative N2O emission by 15.7%-16.8% and 18.1%-18.5% during the growth period of summer maize and winter wheat, respectively. Reduced nitrogen fertilization is an effective way for reducing N2O emission in intensive high-yielding farmland. Under a suitable nitrogen level （200 kg/hm^2）, the application of biochar showed no significant effect on the soil N2O emission in a short term. The N2O emission factors of the L and LF treatments were 0.60% and 0.56%, respectively. ln the intensive high-yield-ing farmland of North China, reducing the nitrogen application amount is an appro-priate measure to mitigate greenhouse gas emissions without crop yield loss.

NiCo_(2)S_(4)@C-N花状电极材料的制备及其在超级电容器中的应用

硫化镍钴(NiCo_(2)S_(4))是一种优良的超级电容器电极材料,具有脆性的晶体结构,容易在循环过程中出现体积膨胀等问题。研究一种NiCo_(2)S_(4)与其他材料负载的异质结构电极材料并应用于超级电容器中至关重要。以Ni(NO_(3))_(2)·6H_(2)O、Co(NO_(3))_(2)·6H_(2)O、硫代乙酰胺(TAA)等为原料,通过一步水热法在碳氮载体上负载NiCo_(2)S_(4)得到NiCo_(2)S_(4)@C-N核壳结构电极材料。采用SEM(扫描电子显微镜)、TEM(透射电子显微镜)、XRD(X射线衍射)、XPS(X射线光电子能谱)对其结构进行表征,证实NiCo_(2)S_(4)在C-N载体上分散均匀且形成具有较大比表面积的核壳结构,促进电子的快速传输。电流密度分别为5 mA/cm^(2)和10 mA/cm^(2)时,NiCo_(2)S_(4)@C-N核壳结构电极材料的比电容分别为250.83 F/g、455.28 F/g。结果表明,在过渡金属硫化物中引入碳氮载体材料构筑核壳结构可以有效提升电化学储能设备的整体电化学性能,NiCo_(2)S_(4)@C-N核壳结构电极材料因其出色的性能特点,有望成为高性能超级电容器电极材料的理想选择。

Effects of Atmospheric CO_2 Enrichment, Applied Nitrogen and Soil Moisture on Dry Matter Accumulation and Nitrogen Uptake in Spring Wheat

Spring wheat (Triticum aestivum L. cv. Dingxi No. 8654) was treated with twoconcentrations of atmospheric CO_2 (350 and 700 μmol mol^(-1)), two levels of soil moisture(well-watered and drought) and five rates of nitrogen fertilizer (0, 50, 100, 150, and 200 mgkg^(-1) soil) to study the atmospheric CO_2 concentration effect on dry matter accumulation and Nuptake of spring wheat. The effects of CO_2 enrichment on the shoot and total mass depended largelyon soil nitrogen level, and the shoot and total mass increased significantly in the moderate to highN treatments but did not increase significantly in the low N treatment. Enriched CO_2 concentrationdid not increase more shoot and total mass in the drought treatment than in the well-wateredtreatment. Thus, elevated CO_2 did not ameliorate the depressive effects of drought and nitrogenstress. In addition, root mass decreased slightly and root/shoot ratio decreased significantly dueto CO_2 enrichment in no N treatment under well-watered condition. Enriched CO_2 decreased shoot Ncontent and shoot and total N uptake; but it reduced root N content and uptake slightly. Shootcritical N concentration was lower for spring wheat grown at 700 μmol mol^(-1) CO_2 than at 350μmol mol^(-1) CO_2 in both well-watered and drought treatments. The critical N concentrations were16 and 19 g kg^(-1) for the well-watered treatment and drought treatment at elevated CO_2 and 21 and26 g kg^(-1) at ambient CO_2, respectively. The reductions in the movement of nutrients to theplant roots through mass flow due to the enhancement in WUE (water use efficiency) and the increasein N use efficiency at elevated CO_2 could elucidate the reduction of shoot and root Nconcentrations.

Closing the nitrogen use efficiency gap and reducing the environmental impact of wheat-maize cropping on smallholder farms in the Guanzhong Plain,Northwest China

A high crop yield with the minimum possible cost to the environment is generally desirable.However,the complicated relationships among crop production,nitrogen(N) use efficiency and environmental impacts must be clearly assessed.We conducted a series of on-farm N application rate experiments to establish the linkage between crop yield and N_2 O emissions in the Guanzhong Plain in Northwest China.We also examined crop yield,partial factor productivity of applied N(PFPN) and reactive N(Nr) losses through a survey of 1 529 and 1 497 smallholder farms that grow wheat and maize,respectively,in the region.The optimum N rates were 175 and 214 kg ha^(-1) for winter wheat and summer maize,respectively,thereby achieving the yields of 6 799 and 7 518 kg ha^(-1),correspondingly,with low N_2 O emissions based on on-farm N rate experiments.Among the smallholder farms,the average N application rates were 215 and 294 kg ha^(-1) season^(-1),thus producing 6 490 and 6 220 kg ha^(-1) of wheat and maize,respectively.The corresponding PFPN values for the two crops were 36.8 and 21.2 kg N kg^(-1),and the total N_2 O emissions were 1.50 and 3.88 kg ha^(-1),respectively.High N balance,large Nr losses and elevated N_2 O emissions could be explained by the overdoses of N application and low grain yields under the current farming practice.The crop yields,N application rates,PFPN and total N_2 O for wheat and maize were 18 and 24% higher,42 and 37% less,75 and 116% higher,and 42 and 47% less,correspondingly,in the high-yield and high-PFPN group than in the average smallholder farms.In conclusion,closing the PFPN gap between the current average and the value for the high-yield and high-PFPN group would increase crop production and reduce Nr losses or the total N_2 O emissions for the investigated cropping system in Northwest China.

Effect of nitrogen fertilization on yield, N content, and nitrogen fixation of alfalfa and smooth bromegrass grown alone or in mixture in greenhouse pots

Planting grass and legume mixtures on improved grasslands has the potential advantage of realizing both higher yields and lower environmental pollution by optimizing the balance between applied N fertilizer and the natural process of legume biological nitrogen fixation. However, the optimal level of N fertilization for grass-legume mixtures, to obtain the highest yield, quality, and contribution of N2 fixation, varies with species. A greenhouse pot experiment was conducted to study the temporal dynamics of N2 fixation of alfalfa （Medicago sativa L.） grown alone and in mixture with smooth bromegrass （Bromus inermis Leyss.） in response to the addition of fertilizer N. Three levels of N （0, 75, and 150 kg ha-1） were examined using 15N-labeled urea to evaluate N2 fixation via the 15N isotope dilution method. Treatments were designated NO （0.001 g per pot）, N75 （1.07 g per pot） and N150 （2.14 g per pot）. Alfalfa grown alone did not benefit from the addition of fertilizer N; dry matter was not significantly increased. In contrast, dry weight and N content of smooth bromegrass grown alone was increased significantly by N application. When grown as a mixture, smooth bromegrass biomass was increased significantly by N application, resulted in a decrease in alfalfa biomass. In addition, individual alfalfa plant dry weight （shoots＋roots） was significantly lower in the mixture than when grown alone at all N levels. Smooth bromegrass shoot and root dry weight were significantly higher when grown with alfalfa than when grown alone, regardless of N application level. When grown alone, alfalfa＇s N2 fixation was reduced with N fertilization （R2=0.9376,P=0.0057）. When grown in a mixture with smooth bromegrass, with 75 kg ha-1 of N fertilizer, the percentage of atmospheric N2 fixation contribution to total N in alfalfa （%Ndfa） had a maximum of 84.07 and 83.05% in the 2nd and 3rd harvests, respectively. Total 3-harvest %Ndfa was higher when alfalfa was grown in a mixture than when grown alone （shoots： ｜t｜=3.39, P=0.0096; root： ｜t｜=3.57, P=0.0073）. We believe this was due to smooth bromegrass being better able to absorb available soil N （due to its fibrous root system）, resulting inlower soil N availability and allowing alfalfa to develop an effective N2 fixing symbiosis prior to the 1st harvest. Once soil N levels were depleted, alfalfa was able to fix N2, resulting in the majority of its tissue N being derived from biological nitrogen fixation （BNF） in the 2nd and 3rd harvests. When grown in a mixture, with added N, alfalfa established an effective symbiosis earlier than when grown alone; in monoculture BNF did not contribute a significant portion of plant N in the N75 and N150 treatments, whereas in the mixture, BNF contributed 17.90 and 16.28% for these treatments respectively. Alfalfa has a higher BNF efficiency when grown in a mixture, initiating BNF earlier, and having higher N2 fixation due to less inhibition by soil-available N. For the greatest N-use-efficiency and sustainable production, grass-legume mixtures are recommended for imDrovino orasslands, usino a moderate amount of N fertilizer （75 kq N ha-l） to provide optimum benefits.

Effects of pre-precipitation of Cr_2N on microstructures and properties of high nitrogen stainless steel

Aging precipitation and solid solution heat treatment were carried out on three steels which have chromium content of 18%, manganese content of 12%, 15%, 18%, and nitrogen content of 0.43%, 0.53%, 0.67%, respectively. The mechanisms of precipitation and solid solution of high nitrogen anstenitic stainless steel were studied using the scanning electron microscopy, transmission electron microscopy, electron probe micro analysis and mechanical testing. The results show that, Cr2N is the primary precipitate in the tested stainless steels instead of Cr23C6. Cr2N nucleates at austenitic grain boundaries and grows towards inner grains with a lameUar morphology. By means of pre-precipitation of Cr2N at 800 ~C, the microstructure of the steels at solid solution state can be refined, thus improving the strength and plasticity. After the proposed treatment, the tensile strength, the proof strength and the elongation of the tested steel reach 881 MPa, 542 MPa and 54%, respectively.

Assessing soil nitrous oxide emission as affected by phosphorus and nitrogen addition under two moisture levels

Agricultural soils are deficient of phosphorus （P） worldwide. Phosphatic fertilizers are therefore applied to agricultural soils to improve the fertility and to increase the crop yield. However, the effect of phosphorus application on soil N2O emissions has rarety been studied. Therefore, we conducted a laboratory study to investigate the effects P addition on soil N2O emissions from P deficient alluvial soil under two levels of nitrogen （N） fertilizer and soil moisture. Treatments were arranged as follows： P （0 and 20 mg P kg-1） was applied to soil under two moisture levels of 60 and 90% water filled pore space （WFPS）. Each P and moisture treatment was further treated with two levels of N fertilizer （0 and 200 mg N kg-1 as urea）. Soil variables including mineral nitrogen （NH4＋-N and NO3--N）, available P, dissolved organic carbon （DOC）, and soil N2O emissions were measured throughout the study period of 50 days. Results showed that addition of P increased N2O emis- sions either under 60% WFPS or 90% WFPS conditions. Higher N2O emissions were observed under 90% WFPS when compared to 60% WFPS. Application of N fertilizer also enhanced N2O emissions and the highest emissions were 141 μg N2O kg-1 h-1 in P＋N treatment under 90% WFPS. The results of the present study suggest that P application markedly increases soil N2O emissions under both low and high soil moisture levels, and either with or without N fertilizer application.

Breaking the linear correlations for enhanced electrochemical nitrogen reduction by carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6)

Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is vital to improve the kinetics of ammonia synthesis and obtain a less energy-intensive process.Herein,carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6) was prepared and applied as an electrocatalyst for high-efficiency NRR.A dramatic faradaic efficiency(FE)of 36.93%and an NH_(3) production rate of 13.1μg h^(-1) mg_(cat)^(-1) were obtained at-0.3 V versus RHE,superior to nearly all Fe-based catalysts.Experiments and DFT calculations revealed that the superior performance was ascribed to the synergistic effect of mixed-valence iron pair,which braked the linear correlations to improve the kinetics of ammonia from collaborative hydrogenation and*NH_(3) separation.This work proves the feasibility of mixedvalence catalysts for nitrogen reduction and thus opening a new avenue towards artificial nitrogenfixation catalysts.

Facile Fabrication of Fe2O3/Nitrogen Deficient g-C3N4-x Composite Catalysts with Enhanced Photocatalytic Performances

The modification of graphitic carbon nitride can significantly improve the photocatalytic performance of graphitic carbon nitride(g-C3N4).Fe2O3/nitrogen-deficient g-C3N4-x composite catalysts were prepared with dicyandiamide as the precursor and Fe3+doped in this study.The composite catalysts were characterized by XRD,SEM,FT-IR,XPS and photocurrent measurements.Close interaction occurred between Fe2O3 and nitrogen deficient g-C3N4-x,more photogenerated electrons were created and effectively separated from the holes,resulting in a decrease of photocarrier recombination,and thus enhancing the photocurrent.Photocatalytic performance experiments showed that Fe2O3/nitrogen deficient g-C3N4-x could utilize lowenergy visible light more efficiently than pure g-C3N4,and the removal rate was 92%in 60 minutes.

Coupled Channels Optical Method Study for Elastic Scattering Process of Electron-N2 Collisions

Different cross sections for the elastic scattering of electrons by N2 at impact energies of 10, 15, 20, 30, 40eV have been calculated and compared with the experimental data and other theoretical results. The present results are obtained by the momentum space coupled channels optical method. In this method, the e-molecule system has a single centre and the interaction of e-nuclei is expanded by a multipole expansion.

Synergetic effect of nitrogen‐doped carbon catalysts for high‐efficiency electrochemical CO_(2) reduction

The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synthesis,cost‐effectiveness,and high conductivity and are ideal electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).However,the unclear identification of the active N sites and the low intrinsic activity of mf‐NCs hinder the further development of high‐performance CO_(2)RR electrocat‐alysts.Achieving precise control over the synthesis of mf‐NC catalysts with well‐defined active N‐species sites is still challenging.To this end,we adopted a facile synthesis method to construct a set of mf‐NCs as robust catalysts for CO_(2)RR.The resulting best‐performing catalyst obtained a Far‐adaic efficiency of CO of approximately 90%at−0.55 V(vs.reversible hydrogen electrode)and good stability.The electrocatalytic performance and in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic N can synergistically adsorb CO_(2) and H_(2)O and thus promote CO_(2) activation and protonation.

Fertilizer nitrogen loss via N_2 emission from calcareous soil following basal urea application of winter wheat

The ratio of nitrous oxide(N2O)to N2O plus nitrogen gas(N2)emitted from soils(N2O/(N2O+N2))is regarded as a key parameter for estimating fertilizer nitrogen(N)loss via N2emission at local,regional or global scales.However,reliable measurement of soil N2emissions is still difficult in fertilized soil-crop systems.In this study,the N loss via N2emission following basal urea application(with a dose of 150 kg N ha-1)to a calcareous soil cultivated with winter wheat was quantified using the helium-based gas-flow-soil-core technique.Emissions of N2and N2O from sampled fresh soils were measured under simulated field soil temperature and oxygen conditions.Our observation performed on the first day after irrigation and rainfall events showed the highest N2and N2O emissions,which amounted to approximately 11.8 and 3.8μg N h-1kg-1dry soil,corresponding to 3304 and 1064μg N m-2h-1,respectively.The N2O/(N2O+N2)molar ratios within about 10 days following fertilization ranged from 0.07 to 0.25,which were much larger than those at the other time.During the one-month experimental period,the urea-N loss via emissions of N2,N2O,and N2+N2O was 1.6%,0.6%,and 2.2%,respectively.Our study confirms that the widely applied acetylene-inhibition method substantially underestimates fertilizer N losses via N2emissions from calcareous soils cultivated with winter wheat.

Ab Initio Quantum Chemistry Study of Nitrogen Cages N_2n(n=12-18)

Ab initio quantum mechanical method has been applied to nitrogen cages N_ 2n (n=12-18). Full geometry optimization, harmonic vibrational frequency and thermodynamics data for eight structures of nitrogen cages N_ 2n (n=12-18) were performed at the HF/cc-pVDZ level. Cage N_ 24 (D_ 6d ), N_ 24 (O_h), N_ 26 (D_ 6d ), N_ 28 (T_d), N_ 30 (D_ 5h ), N_ 32 (D_ 3d ), N_ 36 (D_ 2d ) and N_ 36 (D_ 6h ) were found to be local minima on the potential energy surfaces. The computational results show that all the bond lengths of the eight structures are close to 0.145 nm and their bond energies E_ N-N are near to the experimental data of N-N single-bond. In addition, the thermochemical data of these nitrogen cages indicated that they are stable. It suggests that they are candidates for high energy density materials.

Effects of Different Concentrations of Ammonia Nitrogen on N_2O Emission in the Process of Partial Nitrification

[Objective] The study aimed to discuss the effects of different concentrations of ammonia nitrogen on N2O emission in the process of partial nitrification. [Method] By using a sequencing batch biofilm reactor (SBBR) under intermittent aeration, the influences of various concentrations of influent ammonia nitrogen on nitrous oxide (N2O) emission from partial nitrification were analyzed. [Result] When the concentration of influent ammonia nitrogen varied from 200 to 400 mg/L, the changing trends of DO and ORP value were consistent during the process of partial nitrification, and the concentration ratio of NO-2-N to NH+4-N in effluent water reached 1∶1, with lower NO-3-N level. In addition, ammonia nitrogen concentration in the influent had significant effects on N2O emission in the process of partial nitrification, that is, the higher the ammonia nitrogen concentration, the more the N2O emission. When ammonia nitrogen concentration was 400 mg/L, N2O emission was up to about 37 mg. [Conclusion] N2O emission in the process of partial nitrification might be related to the concentrations of NH+4 and NO-2.

Nitrogen transfer between N_2-fixing plant and non-N_2-fixing plant

The transfer mechanisms. calculating methods and ecological significance of nitrogen transfer between legumes and non-legumes are briefly reviewed. There are three pathways 0f nitrogen transf6r from legumes to neighboring non-legumes: (1) the nitrogen pass in soluble form from the donor legume root into the soil solution, move by diffusion or/and mass flow to the receiver root and be taken up by the latter, (2) nitrogen pass into the soil solution as before, be taken up and transported by mycorrhizal hyphae attached to the receiver roots,(3) if mycorrhizal hyphae form connections (bridges) between the two root systems, the nitrogen could pass into the fungus within the donor root and be transported into the receiver root without ever being in the soil solution. The mechanisms of nitrogen transfer between N2-fixing plants and non-N2-fixing plants are reviewed in terms of indirect and direct pathways. The indirect N-transfer process is related to the release of nitrogen from legumes(donor plants), the possible interaction of this nitrogen with soil, the decomposition and mineralization of legumes and tumover of nitrogen, the nitrogen absorbing and competing abilities of the legume and the non-legume (receiver plant). The direCt nitrogen transfer process is generally considered to be related to the nitrogen gradient and physiological imbalance between legumes and non-legumes, and when the donor legume lies in stressful stage (i.e. removal of shoots or attacked by insects), the nitrogen transfer can be improved significantly. Themethods of deterrnining nitrogen transfer (lndirect 15N-isotope. dilution method and direct 15N determination method) are evaluated, and their advantages and shortcomings are shown in this review.

致密油气窜波及控制体系适用性评价

我国致密油藏分布广泛,储量占比大,开发潜力巨大。此类油藏目前注气开发较多,基质渗透率、孔隙度均较低,油气流动通道主要为裂缝。但油藏裂缝跨尺度发育,受储层非均质性和黏性指进的影响,注气提高采收率技术受限,在裂缝及高渗条带存在时易形成气窜,对地层能量补充带来了诸多问题。选择泡沫和CO_(2)响应性凝胶配制气窜波及控制体系,并通过物理实验模拟评价其性能和在致密油藏的适用性;利用商业数值模拟软件表征CO_(2)注气吞吐及地下成胶反应。经过对国内某致密油藏的数值模拟研究,证明CO_(2)响应性凝胶对注气吞吐有明显的增产效果,采收率增加3.1%,验证了CO_(2)响应性凝胶体系在致密油藏开发中具有良好的应用前景。

压裂液辅助二氧化碳吞吐提高页岩油采收率核磁共振实验

为获取可实现连续补能的页岩油吞吐开发方式,以吉木萨尔页岩油储层为研究对象,借助低频核磁共振岩心分析仪和完成了压裂液辅助CO_(2)吞吐补能一体化模拟实验。分析岩样在多介质吞吐与驱替组合的开发过程中孔喉流体动用特征和采收率变化特征,评价压裂液辅助CO_(2)吞吐提高采收率效果,提出页岩油补能吞吐开发新方式。实验结果表明,CO_(2)吞吐,岩样采收率随吞吐周期快速下降,仅动用中大孔中原油,产油量主要源于前2个周期,最终采收率在30%~40%之间;压裂液辅助CO_(2)吞吐并采用CO_(2)注入端生产,原油主要产自中大孔,且产油量源于前3个周期,最终采收率在30%~40%之间;压裂液辅助CO_(2)吞吐并采用压裂液注入端生产,全部孔隙中原油均得到动用,最终采收率在70%~80%之间,剩余油分布均匀,表现出最好的开发效果。研究可为矿场吞吐补能提高页岩油采收率实践提供一定的理论基础。

电催化氮集成二氧化碳还原反应合成有机氮化合物

以化石能源如煤、石油和天然气为主要能源的社会发展模式,不仅导致不可再生资源枯竭,还引发大气中CO_(2)浓度持续上升的问题。随着人们对能源结构认识的深化和生态环境保护意识的增强,寻求有效的清洁CO_(2)固定和转化技术已成为研究热点。这些技术可利用太阳能、风能、潮汐能和地热能等可再生能源,促进人工碳循环、碳储存,并缓解环境恶化。在众多CO_(2)固定和催化转化技术中,常温常压下的CO_(2)还原技术受到可再生能源的驱动,有助于人工碳循环、碳储存,减轻环境退化。目前,水溶液中的电催化CO_(2)还原研究已取得显著进展,但在制造其他重要的有机小分子,如尿素、酰胺、胺及其衍生物,甚至氨基酸方面,仍有未开发的潜力。这些产品在肥料、化学品合成、医药化学和航空工业等领域有广泛应用,引起了广泛研究兴趣。通过氮集成的电催化CO_(2)还原反应制造有机氮化合物,能显著提高CO_(2)电还原技术的实际应用价值,同时也为生物小分子的起源提供参考,因此具有重要意义。然而,该过程涉及CO_(2)和含氮无机物的电化学耦合,包含多步电子和质子转移过程,因此面临着缓慢的动力学和复杂的反应机制。在本综述中,我们详细讨论了氮集成电催化CO_(2)还原生成不同产物的具体反应路径和合理的催化剂设计策略,这对于指导高效电催化剂的设计至关重要。尽管已经通过一系列策略取得了一定的研究进展,但仍然存在一些需要解决的挑战,这限制了它们在大规模实际应用中的发展。最后,我们对该领域的发展限制和改进的可能方向进行了讨论,希望这能有助于氮集成电催化CO_(2)还原反应催化剂的进一步发展。

钙钛矿结构氧氮化物SrTaO_(2)N的高温高压结构稳定性研究

N2是地球大气的主要组分,N元素是生命起源的基础元素,了解N在地球深部高温高压环境中的赋存形式是探讨全球N循环和宜居性地球大气环境的重要基础。本研究应用金刚石对顶砧(DAC)高压装置和激光加温技术模拟地球深部的压力和温度环境,通过高压原位同步辐射X射线衍射和拉曼光谱对钙钛矿结构氧氮化物SrTaO_(2)N开展高温高压结构稳定性研究。高压X射线衍射结果表明,在0~40.5 GPa的压力范围内,四方结构SrTaO_(2)N没有发生相变,其体积模量为K_(0)=290(3) GPa,并具有a轴和c轴的压缩各向异性。压缩过程中,Ta(O,N)_(6)八面体主要发生刚性旋转,旋转角为0.25°~12.64°,但保持四方结构稳定。常温高压(300 K,40.2 GPa)与高温高压(1800±200 K,41.3 GPa)拉曼对比实验结果显示,在高温高压条件下,SrTaO_(2)N仍保持初始的拉曼谱特征,结构稳定。本研究结果揭示,常压高温条件下通过N^(3-)替代O^(2-)合成的钙钛矿结构氧氮化物,能够在地球内部下地幔上部的温压环境下稳定存在。这种以钙钛矿结构存在的氧氮化物可能是地球深部隐藏的N储库,为解释地球N亏损现象提供了重要线索,同时也为探索N在地球深部中的赋存及其对全球N循环和宜居性大气环境的影响提供了新的研究方向。