Molecular simulation of cage occupancy and selectivity of binary THF–H2 sII hydrate

The hydrogen capacity of the binary THF–H₂ sII hydrate is determined by the cage occupancy and by the selectivity of guest molecules. Grand canonical Monte Carlo (GCMC) simulation is used to study the cage occupancy and selectivity of guest molecules from the equilibrium configuration of the binary sII hydrate. The cage framework is regarded as a rigid body and the number of guest molecules is varied to preserve the grand canonical ensemble. The occupancy and selectivity were investigated at a temperature of 270 K for pressures ranging from 0.1 to 200 MPa. It was found that most large cages select THF as guest molecules while small cages include only hydrogen molecules. Multiple occupancy of hydrogen, up to four molecules in large cages and two molecules in small cages, was found as the pressure increases. GCMC results show that the hydrogen capacity is approximately 1.1 wt% at 200 MPa.     

Molecular dynamics simulation on the decomposition of type SII hydrogen hydrate and the performance of tetrahydrofuran as a stabiliser

Molecular dynamics simulation is used to study the decomposition and stability of SII hydrogen and hydrogen/tetrahydrofuran (THF) hydrates at 150 K, 220 K and 100 bar. The modelling of the microscopic decomposition process of hydrogen hydrate indicates that the decomposition of hydrogen hydrate is led by the diffusive behaviour of H₂ molecules. The hydrogen/THF hydrate presents higher stability, by comparing the distributions of the tetrahedral angle of H₂O molecules, radial distribution functions of H₂O molecules and mean square displacements or diffusion coefficients of H₂O and H₂ molecules in hydrogen hydrate with those in hydrogen/THF hydrate. It is also found that the resistance of the diffusion behaviour of H₂O and H₂ molecules can be enhanced by encaging THF molecules in the (5¹²6⁴) cavities. Additionally, the motion of THF molecules is restricted due to its high interaction energy barrier. Accordingly, THF, as a stabiliser, is helpful in increasing the stability of hydrogen hydrate.     

Molecular dynamics simulation of replacement of methane hydrate with carbon dioxide

Molecular dynamics simulation was performed to analyse the phenomena of replacement of methane hydrate with carbon dioxide (CO₂) at 270 K and 5.0 MPa for 5300 ps. The methane hydrate phase was constructed with 16 unit cells of hydrate. Every cage in the hydrate was occupied by one methane molecule. The methane hydrate phase was sandwiched between two CO₂ phases. During the simulation the hydrate partially melted and liquid water phase appeared, and CO₂ dissolved in the liquid water phase. The replacements were observed three times at the hydrate–liquid water interface during the simulation. In the first case, the replacement occurred at a S-cage without changing the structure. In the second case, an M-cage of methane hydrate partially collapsed, and methane and CO₂ molecules exchanged. After the exchange, the cage occupied by CO₂ remained in the M-cage structure. In the third case, a S-cage of methane hydrate partially collapsed, and methane and CO₂ molecules exchanged. After the exchange, the cage occupied by CO₂ changed to an M-cage-like structure.     

Molecular dynamics simulation of methane hydrate dissociation by depressurisation

Methane (CH₄) hydrate dissociation and the mechanism by depressurisation are investigated by molecular dynamics (MD) simulation. The hydrate decomposition processes are studied by the ‘vacuum removal method’ and the normal method. It is found that the hydrate decomposition is promoted by depressurisation. The quasi-liquid layer is formed in the hydrate surface layer. The driving force of dissociation is found to be controlled by the concentration gradient between the H₂O molecules of the hydrate surface layer and the H₂O molecules of the hydrate inner layer. The clathrates collapse gradually, and the hydrate decomposes layer by layer. Relative to our previous MD simulation results, this study shows that the rate of the hydrate dissociation by depressurisation is slower than that by the thermal stimulation and the inhibitor injection. This study illustrated that MD simulation can play a significant role in investigating the hydrate decomposition mechanisms.     

Four years continuous record of CH4-exchange between the atmosphere and untreated and limed soil of a N-saturated spruce and beech forest ecosystem in Germany

In order to gain information about seasonal and interannual variations of CH₄-fluxes at a spruce control site, a limed spruce site and a beech site of the Höglwald Forest, Bavaria, Germany, complete annual cycles of CH₄-exchange between the soil and the atmosphere with 2-hourly resolution were followed for 4 consecutive years. The ranges of CH₄ fluxes observed for the different sites were: +12.4 to –69.4 g CH₄ m^–2 h^–1 (spruce control site), +11.7 to –51.4 g CH₄ m^–2 h^–1 (limed spruce site), and –4.4 to –167.3 g CH₄ m^–2 h^–1 (beech site). Lowest rates of atmospheric CH₄-uptake or even a weak net-emission of CH₄ by the soils were observed during winter/spring times, whereas highest rates of CH₄-uptake were always found in summer/spring. Over the entire observation period of 4 years, mean CH₄-uptake rates were –1.82 kg CH₄-C ha^–1 yr^–1 at the spruce control site, –1.31 kg CH₄-C ha^–1 yr^–1 at the limed spruce site, and –4.84 kg CH₄-C ha^–1 yr^–1 at the beech site. The results obtained in this study demonstrate that in view of the huge interannual variations in CH₄-fluxes of approx. 1 kg CH₄-C ha^–1 yr^–1, multiple year measurements of CH₄-fluxes are necessary to accurately characterize the sink strength of temperate forest for atmospheric CH₄. By comparison of CH₄-fluxes measured at the spruce control site and the limed spruce site, a significant negative effect of forest floor liming on CH₄-uptake could be demonstrated. Compared to the spruce stand, the beech stand showed on average approx. 3 times higher rates of atmospheric CH₄-uptake, most likely due to pronounced differences between both sites with regard to the organic layer structure and bulk density of the mineral soil. Regression analysis between CH₄-fluxes and environmental parameters revealed that at all sites the dominating factors regulating temporal variations of CH₄ fluxes were soil moisture and soil temperature. Field measurements of CH₄ concentrations in the soil profile and laboratory measurements of CH₄-oxidation and CH₄-production activity on soil samples taken from different soil depths showed that the CH₄-flux at the Höglwald Forest sites is the net-result of simultaneous occurring production and consumption of CH₄ within the soil. Highest CH₄-oxidation activity was found in the uppermost centimeters of the mineral soil, whereas highest potential CH₄-production activity was found in the organic layer.     

Effect of urea fertilizer and environmental factors on CH4 emissions from a Louisiana,USA rice field

Methane emissions from a flooded Louisiana, USA, rice field were measured over the first cropgrowing season. Microplots contained the semidwarf Lemont rice cultivar drill seeded into a Crowley silt loam soil (Typic Albaqualfs). Urea fertilizer was applied preflood at rates of 0, 100, 200 and 300 kg N ha^–1. Emissions of CH₄ from the plots to the atmosphere were measured over a 86-d sampling period until harvest. Methane samples were collected in the morning hours (0730–0930) using a closed-chamber technique. Emissions of CH₄ were highly variable over the first cropping season and a significant urea fertilizer effect was observed. Two peak CH₄ emission periods were observed and occurred about 11 d after panicle differentiation and during the ripening stages. Maximum CH₄ emmissions from the 0, 100, 200 and 300 urea-N treatments were 6.0, 8.9, 9.8 and 11.2 kg CH₄ ha^–1 d^–1, respectively. These flux measurements corresponded to approximately 210, 300, 310 and 360 kg CH₄ evolved ha^–1 over the 86-d sampling period for the 4 treatments.     

The thermal properties of binary structure sI clathrate hydrate from molecular dynamics simulation

In this work, we present temperature dependence of lattice parameter and normalised lattice parameter in the atmospheric pressure and 120 bar and also pressure dependence of unit cell volume and normalised unit cell volume at 150 and 250?K for variety guests with different size, polarity and guest–host hydrogen bonding capability such as trimethylene oxide (TMO), ethylene oxide (EO), formaldehyde (FA), cyclobutane (CB), cyclopropane (CP) and ethane (Et) in the large cages with CH₄ in small cages of sI clathrate hydrates by molecular dynamics simulations. The obtained values of lattice parameters for the guest species are compatible with the experimental values. These clathrate hydrates are simulated with TIP4P/ice four-site water potential. Herein, isobaric thermal expansivity and isothermal compressibility are calculated at a temperature range of 50–250?K and a wide pressure range. These structural properties have been compared for guests which they are isoelectronic and have similar masses but with different size and polarity. We use molecular dynamics simulations to relate microscopic guest properties, like guest–host hydrogen bonding to macroscopic sI clathrate hydrate properties. The temperature dependence of thermodynamic properties such as constant-volume and constant-pressure heat capacity is presented in the atmospheric pressure for these guest species.     

Molecular dynamics simulation of diffusion of hydrogen in binary hydrogen–tetrahydrofuran hydrate

The binary structure II hydrogen–tetrahydrofuran (THF) hydrate was studied with molecular dynamics simulation. The simulations were carried out at 300, 310 K and 10.1 MPa, and with various contents of hydrogen and THF. The migrations of hydrogen molecules from cage to cage were observed. The migration process of hydrogen was also analysed, and the diffusion coefficients of hydrogen in the hydrate were calculated. The calculated diffusion coefficients qualitatively agreed with the experimental data. Double and quintet occupancies of hydrogen molecules were observed in the small and large cages, respectively, without changing the hydrate structure.     

模拟SO42-沉降对闽江口淡水感潮野慈姑湿地甲烷排放通量的影响

2015年12月—2016年10月,每月小潮日原位定期向闽江口塔礁洲淡水感潮野慈姑(Sagittaria trifolia L.)湿地施加剂量为60、120 kg S hm~(-2)a~(-1)的K_2SO_4溶液(分别记做S-60和S-120),探讨模拟硫酸根(SO_4~(2-))沉降对河口淡水感潮湿地甲烷(CH4)排放通量及间隙水SO_4~(2-)浓度的影响。对照、S-60和S-120处理组CH_4排放通量年均值分别为(7.88±1.00)mg h~(-1)m~(-2)、(6.55±0.97)mg h~(-1)m~(-2)和(6.66±1.49)mg h~(-1)m~(-2)。在年尺度上,两个高强度模拟SO_4~(2-)沉降处理组均未显著降低闽江口淡水感潮野慈姑湿地CH_4排放通量(P0.05),即高强度SO_4~(2-)沉降不会对河口淡水感潮湿地CH_4排放通量产生类似于其对泥炭湿地和水稻田的显著抑制效应。在年尺度以及秋、冬季,两个施加K_2SO_4溶液处理显著增加了野慈姑湿地10 cm深度土壤间隙水SO_4~(2-)浓度。对于各个处理组,温度较高的夏、秋季CH_4排放通量均显著高于温度相对较低的冬、春季(P0.05)。不同处理组CH_4排放通量均与土壤温度呈显著正相关关系,温度仍然是影响亚热带河口淡水感潮湿地CH_4排放通量的重要环境因子。     

Exchange of N2O and CH4 between the atmosphere and soils in spruce-fir forests in the northeastern United States

We measured the exchange of N₂O and CH₄ between the atmosphere and soils in 5 spruce-fir stands located along a transect from New York to Maine. Nitrous oxide emissions averaged over the 1990 growing season (May–September) ranged from 2.1 ug N₂O-N/m²-hr in New York to 0.4 ug N₂O-N/m²-hr in Maine. The westernmost sites, Whiteface Mtn., New York and Mt. Mansfield, Vermont, had the highest nitrogen-deposition, net nitrification and N₂O emissions. Soils at all sites were net sinks for atmospheric CH₄ Methane uptake averaged over the 1990 growing season ranged from 0.02 mg CH₄-C/M²-hr in Maine to 0.05 mg CH₄-C/m²-hr in Vermont. Regional differences in CH₄ uptake could not be explained by differences in nitrogen-deposition, soil nitrogen dynamics, soil moisture or soil temperature. We estimate that soils in spruce-fir forests at our study sites released ca. 0.02 to 0.08 kg N₂O-N/ha and consumed ca. 0.74 to 1.85 kg CH₄ C/ha in the 1990 growing season.     

张掖湿地甲烷通量动态特征及其影响因子

于2012年7月—2014年6月对地处干旱区的张掖湿地甲烷(CH_4)通量进行观测,分析其CH_4通量的变化特征及其影响因子。结果表明:CH_4通量的日变化趋势总体表现为白天大于夜间;不同季节CH_4通量排放特征差异明显,夏季最大,春秋次之,冬季最小;CH_4通量日总量与空气温度、土壤温度之间指数相关关系显著,其中4 cm处土壤温度与之相关性最强;1—6月摩擦风速(U*)与CH_4通量显著正相关;结合CO_2通量观测数据,研究时段张掖湿地净碳吸收量为495.92 g C m~(-2)a~(-1),为明显碳汇。     

温带针阔混交林土壤碳氮气体通量的主控因子与耦合关系

中高纬度森林地区由于气候条件变化剧烈,土壤温室气体排放量的估算存在很大的不确定性,并且不同碳氮气体通量的主控因子与耦合关系尚不明确。以长白山温带针阔混交林为研究对象,采用静态箱-气相色谱法连续4a(2005—2009年)测定土壤二氧化碳(CO2)、甲烷(CH4)和氧化亚氮(N2O)净交换通量以及温度、水分等相关环境因子。研究结果表明:温带针阔混交林土壤整体上表现为CO2和N2O的排放源和CH4的吸收汇。土壤CH4、CO2和N2O通量的年均值分别为-1.3 kg CH4hm-2a-1、15102.2 kg CO2hm-2a-1和6.13 kg N2O hm-2a-1。土壤CO2通量呈现明显的季节性规律,主要受土壤温度的影响,水分次之;土壤CH4通量的季节变化不明显,与土壤水分显著正相关;土壤N2O通量季节变化与土壤CO2通量相似,与土壤水分、温度显著正相关。土壤CO2通量和CH4通量不存在任何类型的耦合关系,与N2O通量也不存在耦合关系;土壤CH4和N2O通量之间表现为消长型耦合关系。这项研究显示温带针阔混交林土壤碳氮气体通量主要受环境因子驱动,不同气体通量产生与消耗之间存在复杂的耦合关系,下一步研究需要深入探讨环境变化对其耦合关系的影响以及内在的生物驱动机制。     

Analysis of dissociation process for gas hydrates by molecular dynamics simulation

The dissociation processes of methane and carbon dioxide hydrates were investigated by molecular dynamics simulation. The simulations were performed with 368 water molecules and 64 gas molecules using NPT ensembles. The TraPPE (single-site) and 5-site models were adopted for methane molecules. The EPM2 (3-site) and SPC/E models were used for carbon dioxide and water molecules, respectively. The simulations were carried out at 270 K and 5.0 MPa for hydrate stabilisation. Then, temperature was increased up to 370 K. The temperature increasing rates were 0.1–20 TK/s. The gas hydrates dissociated during increasing temperature or at 370 K. The potential models of methane molecule did not much influence the dissociation process of methane hydrate. The mechanisms of dissociation process were analysed with the coordination numbers and mean square displacements. It was found that the water cages break down first, then the gas molecules escape from the water cages. The methane hydrate was more stable than the carbon dioxide hydrate at the calculated conditions.     

Emission and oxidation of methane in Equisetum fluviatile stands growing on organic sediment and sand bottoms

Methane emission and rhizospheric CH₄ oxidation were studied in stands of Equisetum fluviatile, a common cryptogam in boreal lakes. The experiment was performed in mesocosms with organic sediment or sand bottoms under natural variation of temperature and light using the light-oxic – dark-anoxic chamber (LO/DA) technique. Net CH₄ emission from the organic sediment during the growing season varied between 3.4 and 19.0 mg m^–2 h^–1, but from sand the net CH₄ emission was only 3–10% of that measured from the organic sediment. In the organic sediment net CH₄ emission was very significantly correlated with sediment temperature (r² = 0.92). In the sand mesocosms the variation of net CH₄ emission was better correlated with the shoot biomass than with sediment temperature variation during the growing season, indicating that methanogens were severely limited by substrate availability and were probably dependent on substrates produced by E. fluviatile. The proportion of the methane oxidized of the potential CH₄ emission in summer did not differ significantly between the bottom types. The net CH₄ emission during the growing season as a proportion of the seasonal maximum of the shoot biomass was significantly higher in the organic sediment mesocosms (6.5%) than in sand (1.7%). The high CH₄ emissions observed from dense well-established E. fluviatile stands in the field appear to be more related to temperature-regulated turnover of detritus in the anaerobic sediment and less to CH₄ oxidation and seasonal variation in plant growth dynamics     

Soil gas fluxes of N2O,CH4 and CO2 beneath Lolium perenne under elevated CO2: The Swiss free air carbon dioxide enrichment experiment

Fluxes of nitrous oxide, methane and carbon dioxide were measured from soils under ambient (350 µL L^-1) and enhanced (600 µL L^-1) carbon dioxide partial pressures (pCO₂) at the Free Air Carbon Dioxide Enrichment (FACE) experiment, Eidgenössische Technische Hochschule (ETH), Eschikon, Switzerland in July 1995, using a GC housed in a mobile laboratory. Measurements were made in plots of Lolium perenne maintained under high N input. During the data collection period N fertiliser was applied at a rate of 14 g m^-2 of N. Elevated pCO₂ appeared to result in an increased (27%) output of N₂O, thought to be the consequence of enhanced root-derived available soil C, acting as an energy source for denitrification. The climate, agricultural practices and soils at the FACE experiment combined to give rise to some of the largest N₂O emissions recorded for any terrestrial ecosystem. The amount of CO₂–C being lost from the control plot was higher (10%) than for the enhanced CO₂ plot, and is the reverse of that predicted. The control plot oxidised consistently more CH₄ than the enhanced plot, oxidising 25.5 ± 0.8 µg m^-2 hr^-1 of CH₄ for the control plot, with an average of 8.5 ± 0.4 µg m^-2 hr^-1 of CH₄ for the enhanced CO₂ plot. This suggests that elevated pCO₂ may lead to a feedback whereby less CH₄ is removed from the atmosphere. Despite the limited nature of the current study (in time and space), the observations made here on the interactions of elevated pCO₂ and soil trace gas release suggest that significant interactions are occurring. The feedbacks involved could have importance at the global scale.     

Temperature and urea induced denaturation of the TRP‐cage mini protein TC5b: A simulation study consistent with experimental observations

The effects of temperature and urea denaturation (6M urea) on the dominant structures of the 20‐residue Trp‐cage mini‐protein TC5b are investigated by molecular dynamics simulations of the protein at different temperatures in aqueous and in 6M urea solution using explicit solvent degrees of freedom and the GROMOS force‐field parameter set 45A3. In aqueous solution at 278 K, TC5b is stable throughout the 20 ns of MD simulation and the trajectory structures largely agree with the NMR‐NOE atom–atom distance data available. Raising the temperature to 360 K and to 400 K, the protein denatures within 22 ns and 3 ns, showing that the denaturation temperature is well below 360 K using the GROMOS force field. This is 40–90 K lower than the denaturation temperatures observed in simulations using other much used protein force fields. As the experimental denaturation temperature is about 315 K, the GROMOS force field appears not to overstabilize TC5b, as other force fields and the use of continuum solvation models seem to do. This feature may directly stem from the GROMOS force‐field parameter calibration protocol, which primarily involves reproduction of condensed phase thermodynamic quantities such as energies, densities, and solvation free energies of small compounds representative for protein fragments. By adding 6M urea to the solution, the onset of denaturation is observed in the simulation, but is too slow to observe a particular side‐chain side‐chain contact (Trp6‐Ile4) that was experimentally observed to be characteristic for the denatured state. Interestingly, using temperature denaturation, the process is accelerated and the experimental data are reproduced.     

Methane Budget of a Black Forest Spruce Ecosystem Considering Soil Pattern

Study included seven soils, an adjacent spring and brook and was conducted to estimate CH₄ source and sink strengths of forest soils along a wetness gradient, i.e. their exchange with atmosphere (direct emission), and hydrosphere (indirect emission). Soils are represented by anaerobic Histosol, oxic Cambisols, Histosol with degraded peatlayers and Gleysols having intermediate redox state. They could be separated into three emission groups: CH₄ emitting (248–318 kg C ha⁻¹ a⁻¹), CH₄ uptake (−0.1 to −5 kg C ha⁻¹ a⁻¹), and soils on the edge of CH₄ uptake and release (−0.2–20 kg C ha⁻¹ a⁻¹). Although soils with CH₄ uptake were dominant (75%), the soil specific CH₄ budget identified the study field (6.53 ha) as CH₄ source (40.9 kg C ha⁻¹ a⁻¹). Not only CH₄ emissions, but also dissolved CH₄ in soil solution varied regularly with soil type. Individual soil solutions contained 0.008–151 μmol CH₄ l⁻¹. CH₄ vanished to negligible loads, when dissolved CH₄ passed an oxidative downslope soil zone, but promoted CH₄ uptake was measured at this soil. In turn, CH₄ was discharged to the atmosphere, when the soil solution left the pedosphere across an anaerobic soil zone. These measured indirect emissions were low (34 g C a⁻¹), but the values of individual soil solution indicate possible higher discharges (3.9 kg a⁻¹) at a different soil pattern. The results suggest that CH₄ uptake rates of temperate forests are overestimated.     

冬季水分管理和水稻覆膜栽培对川中丘陵地区冬水田CH4排放的影响

采用静态箱-气相色谱法观测冬季水分管理和水稻覆膜栽培对川中丘陵地区冬水田全年的CH_4排放通量。试验设置持续淹水(CF)、冬季直接落干+稻季淹水(TF)与冬季覆膜落干+稻季覆膜(PM)3个处理。结果表明,冬季休闲期,CF、TF和PM处理CH_4排放分别为16.1、1.4 g/m~2和2.7 g/m~2;水稻生长期,CF、TF和PM处理CH_4排放分别为57.7、27.7 g/m~2和13.5 g/m~2。相较于CF处理,TF与PM处理分别减少其全年CH_4排放60.6%和78.0%。TF与PM处理水稻生长期CH_4排放峰值分别较CF处理低33.0%和56.1%。休闲期,TF、PM处理厢面与厢沟区域CH_4排放与土壤温度显著正相关(P0.05),与土壤氧化还原电位(土壤Eh)显著负相关(P0.05),而CF处理CH_4排放仅与土壤温度显著正相关(P0.05)。水稻生长期,CF处理CH_4排放与土壤温度显著正相关(P0.05),与土壤Eh显著负相关(P0.05),TF处理CH_4排放仅与土壤Eh显著负相关(P0.05),PM处理厢沟CH_4排放与土壤Eh显著正相关(P0.05)。各处理水稻生长期土壤可溶性有机碳含量(DOC)与微生物生物量碳含量(MBC)显著高于休闲期(P0.05)。研究结果为进一步研究冬水田全年CH_4排放规律及寻求有效的减排措施提供数据支撑和科学依据。     

Vegetation heterogeneity and ditches create spatial variability in methane fluxes from peatlands drained for forestry

Drainage of peatlands for forestry starts a succession of ground vegetation in which mire species are gradually replaced by forest species. Some mire plant communities vanish quickly following the water-level drawdown; some may prevail longer in the moister patches of peatland. Drainage ditches, as a new kind of surface, introduce another component of spatial variation in drained peatlands. These variations were hypothesized to affect methane (CH₄) fluxes from drained peatlands. Methane fluxes from different plant communities and unvegetated surfaces, including ditches, were measured at the drained part of Lakkasuo mire, Central Finland. The fluxes were found to be related to peatland site type, plant community, water-table position and soil temperature. At nutrient-rich fen sites fluxes between plant communities differed only a little: almost all plots acted as CH₄ sinks (−0.9 to −0.4 mg CH₄ m⁻² d⁻¹), with the exception of Eriophorum angustifolium Honck. communities, which emitted 0.9 g CH₄ m⁻² d⁻¹. At nutrient-poor bog site the differences between plant communities were clearer. The highest emissions were measured from Eriophorum vaginatum L. communities (29.7 mg CH₄ m⁻² d⁻¹), with a decreasing trend to Sphagna (10.0 mg CH₄ m⁻² d⁻¹) and forest moss communities (2.6 mg CH₄ m⁻² d⁻¹). CH₄ emissions from different kinds of ditches were highly variable, and extremely high emissions (summertime averages 182–600 mg CH₄ m⁻² d⁻¹) were measured from continuously water-covered ditches at the drained fen. Variability in the emissions was caused by differences in the origin and movement of water in the ditches, as well as differences in vegetation communities in the ditches. While drainage on average greatly decreases CH₄ emissions from peatlands, a great spatial variability in fluxes is emerged. Emissions from ditches constantly covered with water, may in some cases have a great impact on the overall CH₄ emissions from drained peatlands.     

The reactivity of tetracarbonylnickel encapsulated in zeolite X. A case history of intrazeolite coordination chemistry.

Zeolite X shows a high capacity for tetracarbonylnickel (up to 28 weight percent) such that complete pore filling with ‘liquid like’ material takes place. The adsorbed material may be removed simply by evacuation at room temperature. Partial decomposition of the Ni(CO)₄ occurs on standing at room temperature under N₂. The resultant orange species is highly reactive and has spectroscopic properties consistent with a coordinatively unsaturated ‘Ni(CO)₃’. Complete and irreversible decomposition by heating to 200 °C in vacuo gives a black zeolite, with an undefined metal phase, which is unreactive towards carbon monoxide. Reaction of the zeolite supported Ni(CO)₄ with various phosphorus ligands is highly dependent on the original loading level as well as the physical size of the ligands involved. At low loadings two kinds of reactivity are observed: 1) With ligands too large to gain access to the zeolite crystal interior, reaction occurs only in solution and so drags the Ni(CO)₄ from the zeolite: 2) With smaller ligands, reaction takes place inside the zeolite cages leading to well-defined, encapsulated, ship-in-bottle complexes which have a stoichiometry dictated by the available space in the cages. At high loading levels, pore blocking phenomena lead to inhomogeneous distributions of encapsulated complexes wherein a complete shell of phosphorous ligand substituted nickel carbonyl species forms at the crystal surface layers and prevents further reaction deeper inside the crystal. The reactivity with large phosphines has been used to study the diffusion of Ni(CO)₄ from the zeolite. Monitoring the appearance of the Ni(CO)₃L (where L = phosphine) by 31-P NMR of the supernatant solution shows that Ni(CO)₄ leaves the zeolite with a first order rate constant of at least 2 × 10^?2 sec^?1 at 298 K.