• Title/Summary/Keyword: Chemical stability

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Surface Characteristics and Spontaneous Combustibility of Coal Treated with Non-polar Solvent under Room Temperature (상온에서의 용매 처리를 통한 저등급 석탄의 표면물성 및 자연발화 특성 변화)

  • Jo, Wan Taek;Choi, Ho Kyung;Kim, Sang Do;Yoo, Ji Ho;Chun, Dong Hyuk;Rhim, Young Joon;Lim, Jeong Hwan;Lee, Si Hyun
    • Korean Chemical Engineering Research
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    • v.51 no.5
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    • pp.609-614
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    • 2013
  • This study investigated the spontaneous combustion behavior of solvent-treated low rank coals. Indonesian lignite (a KBB and SM coal) and sub-bituminous (a Roto coal) were mixed with non-polar 1-methyl naphthalene (1MN) either by mechanical agitation or ultrasonication. The property change associated with 1MN treatment was then analyzed using proximate analysis, calorific value analysis, Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy and moisture re-adsorption test. Susceptibility to spontaneous combustion was evaluated using crossingpoint temperature (CPT) measurement along with gas analysis by GC. A FT-IR profile showed that oxygen functional groups and C-H bonding became weaker when treated by 1 MN. XPS results also indicated a decrease of the oxygen groups (C-O-, C=O and COO-). Increased hydrophobicity was found in the 1MN treated coals during moisture readsorption test. A CPT of the treated coals was ${\sim}20^{\circ}C$ higher than that of the corresponding raw coals and the ultrasonication was more effective way to enhance the stability against spontaneous combustion than the agitation. In the gas analysis less CO and $CO_2$ were emitted from 1MN treated coals, also indicating inhibition of pyrophoric behavior. The surface functional groups participating in the oxidation reaction seemed to be removed by the ultrasonication more effectively than by the simple mechanical agitation.

Spectrophotometric Determination of Soil Chemical Properties Using Soiltek® KA-P Spectrophotometer (Soiltek KA-P 분광광도계률 사용한 토양 화학적 성질의 분광학적 분석)

  • Hyun, Hae-Nam;Oh, Sang-Sil;Koo, Bon-Jun;Kang, Ho-Jun
    • Korean Journal of Soil Science and Fertilizer
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    • v.33 no.2
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    • pp.127-138
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    • 2000
  • To enable rapid and convenient soil test, new soil analytical methods, which require only one instrument, UV/Vis spectrophotometer, were developed and named "Soiltek KA-P spectrophotometric methods". The Soiltek$^{(R)}$ KA-P spectrophotometric method was compared with standard method of RDA in analytical capability for soil chemical properties. Using the 78 soils collected from upland, paddy, orchard, and vinyl house soils, soil organic matter, exchangeable K, Ca, and Mg. CEC, available $SiO_2$, and nitrate were analyzed by the two methods. The color stability(ratio of the absorbance at elapsed time t to the absorbance at time t=0) of organic matter. Ca, Mg, and available $SiO_2$ decreased to about 2% within one hour. However, that of exchangeable K, CEC, and nitrate remained constant. The results obtained with Soiltek$^{(R)}$ KA-P spectrophotometric method showed highly significant correlation with those measured by the standard method of RDA($R^2$ >0.9501), in which the slopes were near unity of $1.0{\pm}0.05$. The standard deviation values of organic matter, exchangeable K, Ca, and Mg, CEC, available $SiO_2$, and nitrate were apparently lower than ${\pm}1.8gkg^{-1}$, ${\pm}0.05cmol^+kg^{-1}$, ${\pm}0.18cmol^+kg^{-1}$, and ${\pm}0.13cmol^+kg^{-1}$, ${\pm}1.0cmol^+kg^{-1}$, ${\pm}5.0mgkg^{-1}$, and ${\pm}10.0mgkg^{-1}$, respectively. All the measurements showed coefficients of variation of less than 7~17% and were within the confidence level of 95%, which means both the methods are precise. Considering the relative simplicity, low cost, precision and accuracy, the proposed Soiltek$^{(R)}$ KA-P spectrophotometric methods could be recommended as an alternative to standard method.

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Swelling and Mechanical Property Change of Shale and Sandstone in Supercritical CO2 (초임계 CO2에 의한 셰일 및 사암의 물성변화 및 스웰링에 관한 연구)

  • Choi, Chae-Soon;Song, Jae-Joon
    • Tunnel and Underground Space
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    • v.22 no.4
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    • pp.266-275
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    • 2012
  • In this study, a method is devised to implement a supercritical $CO_2$ ($scCO_2$) injection environment on a laboratory scale and to investigate the effects of $scCO_2$ on the properties of rock specimens. Specimens of shale and sandstone normally constituting the cap rock and reservoir rock, respectively, were kept in a laboratory reactor chamber with $scCO_2$ for two weeks. From this stage, a chemical reaction between rock surface and the $scCO_2$ was induced. The effect of saline water was also investigated by comparing three conditions ($scCO_2$-rock, $scCO_2-H_2O$-rock and $scCO_2$-brine(1M)-rock). Finally, we checked the changes in the properties before and after the reaction by destructive and nondestructive testing procedures. The swelling of shale was a main concern in this case. The experimental results suggested that $scCO_2$ has a greater effect on the swelling of the shale than pure water and brine. It was also observed that the largest swelling displacement of shale occurred after a reaction with the $H_2O-scCO_2$ solution. The results of a series of the destructive and nondestructive tests indicate that although each of the property changes of the rock differed depending on the reaction conditions, the $H_2O-scCO_2$ solution had the greatest effect. In this study, shale was highly sensitive to the reaction conditions. These results provide fundamental information pertaining to the stability of $CO_2$ storage sites due to physical and chemical reactions between the rocks in these sites and $scCO_2$.

Oxidative Desulfurization of Marine Diesel Using Keggin Type Heteropoly Acid Catalysts (Keggin형 헤테로폴리산 촉매를 이용한 선박용 경유의 산화 탈황)

  • Oh, Hyeonwoo;Woo, Hee Chul
    • Clean Technology
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    • v.25 no.1
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    • pp.91-97
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    • 2019
  • Oxidative desulfurization (ODS) has received much attention in recent years because refractory sulfur compounds such as dibenzothiophenes can be oxidized selectively to their corresponding sulfoxides and sulfones, and these products can be removed by extraction and adsorption. In this work, The oxidative desulfurization of marine diesel fuel was performed in a batch reactor with hydrogen peroxide ($H_2O_2$) in the presence of various supported heteropoly acid catalysts. The catalysts were characterized by XRD, XRF, XPS and nitrogen adsorption isotherm techniques. Based on the sulfur removal efficiency of promising silica supported heteropoly acid catalysts, the ranking of catalytic activity was: $30\;H_3PW_{12}/SiO_2$ > $30\;H_3PMo_{12}/SiO_2$ > $30\;H_4SiW_{12}/SiO_2$, which appears to be related with their intrinsic acid strength. The $30\;H_3PW_{12}/SiO_2$ catalyst showed the highest initial sulfur removal efficiency of about 66% under reaction conditions of $30^{\circ}C$, $0.025g\;mL^{-1}$ (cat./oil), 1 h reaction time. However, through the recycle test of the $H_3PW_{12}/SiO_2$ catalyst, significant deactivation was observed, which was attributed to the elution of the active component $H_3PW_{12}$. By introducing cesium cation ($Cs^+$) into the $H_3PW_{12}/SiO_2$ catalyst, the stability of the catalyst was improved with changing the solubility, and the $Cs^+$ ion exchanged catalyst could be recycled for at least five times without severe elution.

Study of HubWA Protein Folding Reaction by Measuring the Stability of Folding Intermediate (중간단계의 구조적 안정성을 통한 HubWA 단백질의 접힘(folding) 반응 탐색)

  • Soon-Ho Park
    • Journal of the Korean Chemical Society
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    • v.67 no.2
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    • pp.81-88
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    • 2023
  • The contribution of hydrophobic residues to the protein folding reaction was studied by using HubWA variant proteins with I and L to V mutation. Folding kinetics of all V variant proteins was observed to be satisfied by a three-state on-pathway mechanism, U ⇌ I ⇌ N, where U, I, and N represent unfolded, intermediate, and native state, respectively. Three-state folding reaction was quantitatively analyzed and the free energy of folding of each elementary reactions and overall folding reaction, ΔGoUI, ΔGoIN, and ΔGoUN, were obtained. From the ratio of free energy difference between the variant protein and HubWA, ΔΔGoUI/ΔΔGoUN (ΔΔGoUI = ΔGoUI (variant protein) - ΔGoUI (HubWA) and ΔΔGoUN = ΔGoUN (variant protein) - ΔGoUN(HubWA)), the contribution of hydrophobic residues to HubWA folding was analyzed. The residues which are located in the hydrophobic core between α-helix and β-sheet, I3, I13, L15, I30, L43, I61 and L67, showed ΔΔGoUI/ΔΔGoUN value of ~0.5 when each of these residues was mutated to V, indicating that these residues form relatively solid hydrophobic core in the intermediate state. Residues located at the end of secondary structures and loop, I23, L69 and I36 showed ΔΔGoUI/ΔΔGoUN value below 0.4 when each of these residues was mutated to V, indicating that the region containing these residues are loosely formed in the intermediate state. V17A, L50V and L56V showed fairly high ΔΔGoUI/ΔΔGoUN value of ~0.8. Since L50 and L56 are located in the region containing long loop (residue 46 to 62), it is suggested that the high ΔΔGoUI/ΔΔGoUN value of these residues prevents the formation of aggregate at the early stage of folding reaction.

Arsenic Removal Mechanism of the Residual Slag Generated after the Mineral Carbonation Process in Aqueous System (광물탄산화 공정 이후 발생하는 잔사슬래그의 수계 내 비소 제거 기작)

  • Kim, Kyeongtae;Latief, Ilham Abdul;Kim, Danu;Kim, Seonhee;Lee, Minhee
    • Economic and Environmental Geology
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    • v.55 no.4
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    • pp.377-388
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    • 2022
  • Laboratory-scale experiments were performed to identify the As removal mechanism of the residual slag generated after the mineral carbonation process. The residual slags were manufactured from the steelmaking slag (blast oxygen furnace slag: BOF) through direct and indirect carbonation process. RDBOF (residual BOF after the direct carbonation) and RIBOF (residual BOF after the indirect carbonation) showed different physicochemical-structural characteristics compared with raw BOF such as chemical-mineralogical properties, the pH level of leachate and forming micropores on the surface of the slag. In batch experiment, 0.1 g of residual slag was added to 10 mL of As-solution (initial concentration: 203.6 mg/L) titrated at various pH levels. The RDBOF showed 99.3% of As removal efficiency at initial pH 1, while it sharply decreased with the increase of initial pH. As the initial pH of solution decreased, the dissolution of carbonate minerals covering the surface was accelerated, increasing the exposed area of Fe-oxide and promoting the adsorption of As-oxyanions on the RDBOF surface. Whereas, the As removal efficiency of RIBOF increased with the increase of initial pH levels, and it reached up to 70% at initial pH 10. Considering the PZC (point of zero charge) of the RIBOF (pH 4.5), it was hardly expected that the electrical adsorption of As-oxyanion on surface of the RIBOF at initial pH of 4-10. Nevertheless it was observed that As-oxyanion was linked to the Fe-oxide on the RIBOF surface by the cation bridge effect of divalent cations such as Ca2+, Mn2+, and Fe2+. The surface of RIBOF became stronger negatively charged, the cation bridge effect was more strictly enforced, and more As can be fixed on the RIBOF surface. However, the Ca-products start to precipitate on the surface at pH 10-11 or higher and they even prevent the surface adsorption of As-oxyanion by Fe-oxide. The TCLP test was performed to evaluate the stability of As fixed on the surface of the residual slag after the batch experiment. Results supported that RDBOF and RIBOF firmly fixed As over the wide pH levels, by considering their As desorption rate of less than 2%. From the results of this study, it was proved that both residual slags can be used as an eco-friendly and low-cost As remover with high As removal efficiency and high stability and they also overcome the pH increase in solution, which is the disadvantage of existing steelmaking slag as an As remover.

A Study on the Preparation of Traditional Andong sikhe with Lactic Acid Bacteria (유산균을 이용한 전통안동식혜의 제조방법에 관한 연구)

  • Choi, Cheong;Son, Gyu-Mok
    • Journal of the Korean Society of Food Culture
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    • v.7 no.3
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    • pp.259-270
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    • 1992
  • The changes in life style today appear many ways. Many housewives turn away from home preparation of the time consuming traditional foods, such as 'Andong sikhe'. The importance, however, of succeeding the traditional cuisines is getting appreciated widely nowadays. This study aimed to investigate the preparation of Andong sikhe by use of pure culture inoculation and the improvement of storage stability by the addition of stabilizers to the product. Lactobacillus delbreuckii was selected for the pure culture inoculation in the fermentation. The changes in chemical composition such as total acidity, sugar content, amino acid and various forms of nitrogen during fermentation were determined. The changes in pH of the product, the enzyme activities and the population of lactic acid bacteria were also followed in the process of fermentation. The Lactobacillus dominated in the beginning of the fermentation but the Streptococcus out numbered the former as the fermentation proceeded. The crude protein content increased up to the 4th day of fermentation but slowly decreased there after. The pH of the product rapidly decreased to 4.2 by the 2nd day of fermentation. The total acidity reached to the 0.38% by the 2nd day of fermentation and kept on increasing slowly during the fermentation. The free sugar consisted of 6 kinds including maltose and one unknown sugar. The amino form nitrogen increased up to 38.5mg% at the 2nd day of fermentation and the product tasted best at this time. The ammonia form nitrogen, water soluble and salt soluble protein decreased during fermentation. Proline and aspartic acid were the two major free amino acids. The free methionine increased while the free lysine decreased in the process of fermentation. The major amino acids of water soluble and salt soluble protein were glutamic acid and aspartic acid. The arginine content of salt soluble protein increased as the fermentation proceeded. Linoleic, palmitic and oleic acid were the three major fatty acids and occupy 90% or more of the total fatty acids. The activities of acid protease and liquefying amylase reached to the maximum at the 4th day of fermentation while those of saccharogenic amylase and lipase reached to the peak at the 2nd day of fermentation.

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Changes of Chemical Components during Fermentation of Pear Wine (배술 발효 과정 중 화학 성분의 변화)

  • Lee, Ka-Soon;Park, Hae-Min;Hong, Jong-Sook;Lee, Gyu-Hee;Oh, Man-Jin
    • Food Science and Preservation
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    • v.16 no.6
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    • pp.991-998
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    • 2009
  • We used pears to manufacture wine, and analyzed changes in pH, acidity and ethanol and sugar content during fermentation. Pear wine with added ginger (to improve quality) did not differ from ginger-free wine in pH or acidity level. The ethanol content of pear wine was the highest (13.0%, v/v) inpear wine with 0.1% (w/v) added ginger compared to pear wine with no ginger, and sensory tests examining taste and color yielded the highest scores for pear wine with 0.2% (w/v) ginger. To assess storage stability, pear wine was treated for 30 minutes at $55^{\circ}C$, $60^{\circ}C$, $65^{\circ}C$, or $70^{\circ}C$. Unheated pear wine showed rapid changes in pH and acidity level after 30 days of storage, whereas pear wine treated for 30 minutes at $60^{\circ}C$ did not show such changes. Total organic acid levels in pear wine increased by 0.71% and 0.89% (v/v), respectively. The free sugar level in pear wine decreased from 12.05% to 3.13% (w/v). Turning to phenolic compounds, caffeic acid, catechin, and epicatechin contents in pears were 1.64, 1.40, and 0.23 mg/100mL, respectively, with diverse compositions. Caffeic acid levels in pear wine decreased sharply to 0.12 mg/100 mL upon fermentation, whereas free catechin inpear wine increased to 1.16 mg/100 mL compared with 0.28 mg/100 mL in pears. Free arbutin increased from 8.34 mg/100 mL in pears to 10.39 mg/100 mL in pear wine. The free amino acid content of pear wine was 118.5 g/100 mL, but the levels of serine, alanine, glutamic acid, and aspartic acid decreased sharply upon fermentation, with corresponding increases in tyrosine, GABA, lysine, and arginine.

Highly Doped Nano-crystal Embedded Polymorphous Silicon Thin Film Deposited by Using Neutral Beam Assisted CVD at Room Temperature

  • Jang, Jin-Nyeong;Lee, Dong-Hyeok;So, Hyeon-Uk;Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.154-155
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    • 2012
  • The promise of nano-crystalites (nc) as a technological material, for applications including display backplane, and solar cells, may ultimately depend on tailoring their behavior through doping and crystallinity. Impurities can strongly modify electronic and optical properties of bulk and nc semiconductors. Highly doped dopant also effect structural properties (both grain size, crystal fraction) of nc-Si thin film. As discussed in several literatures, P atoms or radicals have the tendency to reside on the surface of nc. The P-radical segregation on the nano-grain surfaces that called self-purification may reduce the possibility of new nucleation because of the five-coordination of P. In addition, the P doping levels of ${\sim}2{\times}10^{21}\;at/cm^3$ is the solubility limitation of P in Si; the solubility of nc thin film should be smaller. Therefore, the non-activated P tends to segregate on the grain boundaries and the surface of nc. These mechanisms could prevent new nucleation on the existing grain surface. Therefore, most researches shown that highly doped nc-thin film by using conventional PECVD deposition system tended to have low crystallinity, where the formation energy of nucleation should be higher than the nc surface in the intrinsic materials. If the deposition technology that can make highly doped and simultaneously highly crystallized nc at low temperature, it can lead processes of next generation flexible devices. Recently, we are developing a novel CVD technology with a neutral particle beam (NPB) source, named as neutral beam assisted CVD (NBaCVD), which controls the energy of incident neutral particles in the range of 1~300eV in order to enhance the atomic activation and crystalline of thin films at low temperatures. During the formation of the nc-/pm-Si thin films by the NBaCVD with various process conditions, NPB energy directly controlled by the reflector bias and effectively increased crystal fraction (~80%) by uniformly distributed nc grains with 3~10 nm size. In the case of phosphorous doped Si thin films, the doping efficiency also increased as increasing the reflector bias (i.e. increasing NPB energy). At 330V of reflector bias, activation energy of the doped nc-Si thin film reduced as low as 0.001 eV. This means dopants are fully occupied as substitutional site, even though the Si thin film has nano-sized grain structure. And activated dopant concentration is recorded as high as up to 1020 #/$cm^3$ at very low process temperature (< $80^{\circ}C$) process without any post annealing. Theoretical solubility for the higher dopant concentration in Si thin film for order of 1020 #/$cm^3$ can be done only high temperature process or post annealing over $650^{\circ}C$. In general, as decreasing the grain size, the dopant binding energy increases as ratio of 1 of diameter of grain and the dopant hardly be activated. The highly doped nc-Si thin film by low-temperature NBaCVD process had smaller average grain size under 10 nm (measured by GIWAXS, GISAXS and TEM analysis), but achieved very higher activation of phosphorous dopant; NB energy sufficiently transports its energy to doping and crystallization even though without supplying additional thermal energy. TEM image shows that incubation layer does not formed between nc-Si film and SiO2 under later and highly crystallized nc-Si film is constructed with uniformly distributed nano-grains in polymorphous tissues. The nucleation should be start at the first layer on the SiO2 later, but it hardly growth to be cone-shaped micro-size grains. The nc-grain evenly embedded pm-Si thin film can be formatted by competition of the nucleation and the crystal growing, which depend on the NPB energies. In the evaluation of the light soaking degradation of photoconductivity, while conventional intrinsic and n-type doped a-Si thin films appeared typical degradation of photoconductivity, all of the nc-Si thin films processed by the NBaCVD show only a few % of degradation of it. From FTIR and RAMAN spectra, the energetic hydrogen NB atoms passivate nano-grain boundaries during the NBaCVD process because of the high diffusivity and chemical potential of hydrogen atoms.

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Transition Metal Dichalcogenide Nanocatalyst for Solar-Driven Photoelectrochemical Water Splitting (전이금속 디칼코제나이드 나노촉매를 이용한 태양광 흡수 광화학적 물분해 연구)

  • Yoo, Jisun;Cha, Eunhee;Park, Jeunghee;Lim, Soo A
    • Journal of the Korean Electrochemical Society
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    • v.23 no.2
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    • pp.25-38
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    • 2020
  • Photoelectrochemical water splitting has been considered as the most promising technology for generating hydrogen energy. Transition metal dichalcogenide (TMD) compounds have currently attracted tremendous attention due to their outstanding ability towards the catalytic water-splitting hydrogen evolution reaction (HER). Herein, we report the synthesis method of various transition metal dichalcogenide including MoS2, MoSe2, WS2, and WSe2 nanosheets as excellent catalysts for solar-driven photoelectrochemical (PEC) hydrogen evolution. Photocathodes were fabricated by growing the nanosheets directly onto Si nanowire (NW) arrays, with a thickness of 20 nm. The metal ion layers were formed by soaking the metal chloride ethanol solution and subsequent sulfurization or selenization produced the transition metal chalcogenide. They all exhibit excellent PEC performance in 0.5 M H2SO4; the photocurrent reaches to 20 mA cm-2 (at 0 V vs. RHE) and the onset potential is 0.2 V under AM1.5 condition. The quantum efficiency of hydrogen generation is avg. 90%. The stability of MoS2 and MoSe2 is 90% for 3h, which is higher than that (80%) of WS2 and WSe2. Detailed structure analysis using X-ray photoelectron spectroscopy for before/after HER reveals that the Si-WS2 and Si-WSe2 experience more oxidation of Si NWs than Si-MoS2 and Si-MoSe2. This can be explained by the less protection of Si NW surface by their flake shape morphology. The high catalytic activity of TMDs should be the main cause of this enhanced PEC performance, promising efficient water-splitting Si-based PEC cells.